Liquid composition, spray product, aerosol product

Abstract

Provided are: a liquid composition in which ultra-fine bubbles (ultra-fine bubbles) are stably dispersed at a high concentration for a long period of time; and a discharge product. A liquid composition in which ultra-fine bubbles are dispersed, the particle diameter (D90) of the ultra-fine bubbles having a volume cumulative distribution value of 90% being 50-300 nm, and the number of the ultra-fine bubbles being 4.0 * 107 or more per milliliter.

Description

Technical Field

[0001] This invention relates to a liquid composition, a sprayed product, and an aerosol product. More specifically, this invention relates to a liquid composition and a sprayed product in which ultrafine bubbles (microbubbles) are dispersed at a high concentration and stably over a long period of time. Furthermore, this invention relates to an aerosol product capable of generating ultrafine bubbles (microbubbles) at a high concentration, and where the particle size distribution width of the ultrafine bubbles is reduced. Background Technology

[0002] Previously, methods for dispersing nanoscale (1–1000 nm) bubbles in liquids have been developed. Patent Document 1 discloses a method and apparatus for generating microbubbles using an aerosol container. The generating apparatus in Patent Document 1 can spray liquid containing microbubbles with a particle size of approximately 50–1000 nm by filling an aerosol container with a liquid mainly composed of water and spraying a gas (nitrogen) and using a spray button with a flow adjustment mechanism.

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2021 / 085628 Summary of the Invention However, according to the generating device described in Patent Document 1, the flow rate adjustment mechanism uses a piston and spring to adjust the flow rate in order to maintain a constant spray state. Therefore, the generated bubbles have a particle size of 50–1000 nm, showing a wide range. In microbubbles, if there are many large-sized bubbles, it is difficult to retain them in the liquid, and the bubbles easily disappear. As a result, the generating device described in Patent Document 1 cannot achieve a high concentration and long-term stable dispersion of microbubbles.

[0004] This invention differs from such prior art in that it aims to provide a liquid composition and a spray product in which ultrafine bubbles are dispersed at a high concentration and stably over a long period of time. Furthermore, this invention aims to provide an aerosol product capable of generating ultrafine bubbles at a high concentration in a spray, and where the particle size distribution width of the ultrafine bubbles is reduced.

[0005] The liquid composition related to one aspect of the present invention for solving the above-mentioned problems is a liquid composition in which ultrafine bubbles are dispersed, wherein the ultrafine bubbles have a particle size D90 of 50-300 nm with a 90% volumetric cumulative distribution value, and the number of ultrafine bubbles is 4.0 × 10⁻⁶ per milliliter. 7 More than one.

[0006] In addition, one aspect of the present invention related to solving the above-mentioned problems is a spray product made by filling the above-mentioned liquid composition into a spray container.

[0007] Furthermore, the aerosol product related to one aspect of the present invention that solves the above-mentioned problems is an aerosol product for spraying a liquid composition, wherein the liquid composition is a liquid composition dispersed with ultrafine bubbles, the ultrafine bubbles having a volumetric cumulative distribution value of 90% and a particle size D90 of 50–300 nm, and the number of ultrafine bubbles is 4.0 × 10⁻⁶ per milliliter. 7 The aerosol product comprises an aerosol container filled with a stock solution and a propellant, and a spray button installed in the aerosol container and having a spray hole formed thereon. When the propellant is sprayed from the spray hole, the spray force at a distance of 5 cm from the spray hole is 10 to 400 mN. Attached Figure Description

[0008] Figure 1 This is a schematic cross-sectional view of an aerosol product of a liquid composition used in one embodiment (first embodiment) of the present invention.

[0009] Figure 2 This is a schematic diagram illustrating one embodiment of the ejection member used to produce an aerosol product of a liquid composition according to one embodiment of the present invention.

[0010] Figure 3 This is a schematic diagram illustrating one embodiment of the ejection member used to produce an aerosol product of a liquid composition according to one embodiment of the present invention.

[0011] Figure 4 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition after 15 minutes of spraying in Example A1.

[0012] Figure 5 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition after 1 day of spraying in Example A1.

[0013] Figure 6 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition 15 minutes after spraying in Example A3.

[0014] Figure 7 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition after 1 day of spraying in Example A3.

[0015] Figure 8 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition after 15 minutes of spraying in Example A5.

[0016] Figure 9This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition one day after spraying in Example A5.

[0017] Figure 10 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Comparative Example A1.

[0018] Figure 11 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition after 15 minutes of spraying in Example A7.

[0019] Figure 12 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition one day after spraying in Example A7.

[0020] Figure 13 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Comparative Example A2.

[0021] Figure 14 This is a schematic cross-sectional view of an aerosol product of a liquid composition used in one embodiment (second embodiment) of the present invention.

[0022] Figure 15 This is a cross-sectional view of an ejection component for producing an aerosol product of a liquid composition according to an embodiment of the present invention.

[0023] Figure 16 This is a cross-sectional view of the ejection component used to produce an aerosol product of a liquid composition according to an embodiment of the present invention.

[0024] Figure 17 This is a graph showing the relationship between particle size and concentration of the liquid composition after 15 minutes of spraying in Example B1.

[0025] Figure 18 This is a graph showing the relationship between particle size and concentration of the liquid composition after one day of spraying in Example B1.

[0026] Figure 19 This is a graph showing the relationship between particle size and concentration of the liquid composition after 15 minutes of spraying in Example B6.

[0027] Figure 20 This is a graph showing the relationship between particle size and concentration of the liquid composition after 1 day of spraying in Example B6.

[0028] Figure 21 This is a graph showing the relationship between particle size and concentration of the liquid composition of Comparative Example B1 after 15 minutes of spraying.

[0029] Figure 22This is a graph showing the relationship between particle size and concentration of the liquid composition of Comparative Example B2 after 15 minutes of spraying.

[0030] Figure 23 This is a graph showing the relationship between particle size and concentration of the liquid composition of Comparative Example B3 after 15 minutes of spraying.

[0031] Figure 24 This is a graph showing the relationship between particle size and concentration of the liquid composition after 15 minutes of spraying in Example B8.

[0032] Figure 25 This is a graph showing the relationship between particle size and concentration of the liquid composition of Comparative Example B4 after 15 minutes of spraying.

[0033] Figure 26 This is a graph showing the relationship between particle size and concentration of the liquid composition of Comparative Example B5 after 15 minutes of spraying.

[0034] Figure 27 This is a schematic diagram illustrating one embodiment of the ejection member 8a used to manufacture the aerosol products of the liquid compositions of Examples B11 and B12 of the present invention.

[0035] Figure 28 This is a graph showing the relationship between particle size and concentration of the liquid composition after 15 minutes of spraying in Example B10.

[0036] Figure 29 This is a graph showing the relationship between particle size and concentration of the liquid composition after 15 minutes of spraying in Example B11.

[0037] Figure 30 This is a graph showing the relationship between particle size and concentration of the liquid composition after 15 minutes of spraying in Example B14.

[0038] Figure 31 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C1 was sprayed.

[0039] Figure 32 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C2 was sprayed.

[0040] Figure 33 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the aerosol product of Example C3.

[0041] Figure 34 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C4 was sprayed.

[0042] Figure 35 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the aerosol product of Example C5.

[0043] Figure 36 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the aerosol product of Example C6.

[0044] Figure 37 This is a graph showing the relationship between particle size and concentration of the liquid (water) in Comparative Example C1.

[0045] Figure 38 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the product of Comparative Example C2.

[0046] Figure 39 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the aerosol product of Comparative Example C3.

[0047] Figure 40 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C7 was sprayed.

[0048] Figure 41 This is a graph showing the relationship between particle size and concentration of the liquid (ethanol) in Comparative Example C4.

[0049] Figure 42 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the product of Comparative Example C5.

[0050] Figure 43 This is a schematic diagram illustrating one embodiment of the spray button 8a used to manufacture the aerosol products of Examples C10 and C11.

[0051] Figure 44 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C9 was sprayed.

[0052] Figure 45 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the aerosol product of Example C10.

[0053] Figure 46 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C13 was sprayed.

[0054] Figure 47 This is a graph showing the relationship between the particle size and concentration of the sprayed material 15 minutes after the aerosol product of Example C14 was sprayed.

[0055] Figure 48 This is a graph showing the relationship between the particle size and concentration of the sprayed material after 15 minutes of spraying the aerosol product of Example C15. Detailed Implementation

[0056] <Liquid Composition> The liquid composition of the present invention is a liquid composition in which ultrafine bubbles are dispersed. The particle size D90 of the ultrafine bubbles, with a 90% volumetric cumulative distribution value, is 50–300 nm. The number of ultrafine bubbles in the liquid composition is 4.0 × 10⁻⁶ per milliliter. 7 More than one. Hereinafter, an example of a preferred embodiment of the present invention will be described.

[0057] [First Implementation] In the liquid composition of this embodiment (first embodiment) of the present invention, the ultrafine bubbles are bubbles formed by the vaporization of liquefied gas that has become gas at 25°C and atmospheric pressure, and the number of ultrafine bubbles is preferably 5.0 × 10⁻⁶ per milliliter. 7 More than one.

[0058] (liquid) There are no particular limitations on the liquids constituting the liquid composition. As an example, the liquid may contain various aqueous solvents and oily solvents as main components. More specifically, aqueous solvents include water such as purified water, ion-exchanged water, physiological saline, and deep-sea water; or monohydric alcohols with 2 to 3 carbon atoms such as ethanol and isopropanol, and polyhydric alcohols with 2 to 3 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, and glycerol; as well as mixtures of water and alcohols. Oily solvents include ester oils such as isopropyl myristate, isopropyl palmitate, diisopropyl adipate, caprylic / capric triglyceride, diethoxyethyl succinate, methylpentyl glycol dipentanoate, and neopentyl glycol didecanoate; hydrocarbon oils such as flowing paraffin, kerosene, squalene, squalane, and isoparaffin; and oils such as avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, sesame oil, castor oil, flaxseed oil, safflower oil, jojoba oil, wheat germ oil, coconut oil, and palm oil. Esters; silicone oils such as polysiloxane, methylphenyl polysiloxane, and methyl polycyclosiloxane; hydrofluoroolefins with boiling points of 5–40°C, such as trans-1-chloro-3,3,3-trifluoropropylene (HFO-1233zd(E), boiling point 19°C), cis-1-chloro-3,3,3-trifluoropropylene (HFO-1233zd(Z), boiling point 39°C), and cis-1-chloro-2,3,3,3-tetrafluoroolefin (HFO-1224yd(Z), boiling point 15°C). The components listed in the aqueous or oil-based solvents can also be added to the solvent as additives or active ingredients.

[0059] The solvent content is preferably 60% by mass or more in the liquid, more preferably 70% by mass or more. Furthermore, the solvent content is preferably 100% by mass or less in the liquid, more preferably 99.9% by mass or less. By keeping the solvent content within the above range, the ultrafine bubbles of the liquefied gas have small particle sizes and are easily and stably dispersed over a long period. In particular, when the liquid contains 60% by mass or more of water, the ultrafine bubbles in the liquid composition have small particle sizes and a narrower particle size distribution width, resulting in uniform ultrafine particle size and a sustained stable effect.

[0060] (Ultra-fine bubbles) Ultrafine bubbles are tiny bubbles dispersed in a liquid.

[0061] The particle size D90, where the volumetric cumulative distribution value of the ultrafine bubbles is 90%, can be 50 nm or more, preferably 70 nm or more. Furthermore, the particle size D90, where the volumetric cumulative distribution value of the ultrafine bubbles is 90%, can be 300 nm or less, preferably 250 nm or less. By ensuring that D90 is within the above range, the liquid composition contains a majority of tiny bubbles with an average particle size in the nanometer range (1–1000 nm), particularly ultrafine bubbles of 10–300 nm. As a result, the obtained liquid composition has high transparency, and the ultrafine bubbles can be dispersed at a high concentration and stably for a long period.

[0062] Furthermore, in this embodiment, the particle size D90 with a cumulative distribution value of 90% can be measured, for example, using a nano-tracking particle size measuring device (NanoSight NS300, manufactured by Malvern Panalytical Ltd) to measure a liquid composition adjusted to 25°C.

[0063] According to the aforementioned nano-tracking particle size measuring device, in addition to D90, the particle size D50 with a cumulative distribution value of 50% and the particle size D10 with a cumulative distribution value of 10% can also be measured. Furthermore, the nano-tracking particle size measuring device can also measure the number of ultrafine bubbles per milliliter.

[0064] The D50 of the ultrafine bubbles is preferably 30 nm or more, more preferably 50 nm or more. Furthermore, the D50 of the ultrafine bubbles is preferably 200 nm or less, more preferably 170 nm or less. Furthermore, the D10 of the ultrafine bubbles is preferably 10 nm or more, more preferably 20 nm or more. Furthermore, the D10 of the ultrafine bubbles is preferably 150 nm or less, more preferably 120 nm or less. By keeping the D50 and D10 within the above ranges, in the liquid composition, ultrafine bubbles with an average particle size of nanometers (1–1000 nm) constitute the majority, particularly ultrafine bubbles with a D90 of 10–300 nm. As a result, the obtained liquid composition has high transparency, and the ultrafine bubbles can be dispersed at a high concentration and stably for a long period.

[0065] In the ultrafine bubbles of this embodiment, the proportion of bubbles with a particle size exceeding 300 nm is preferably 10% or less of the total number of bubbles, more preferably 5% or less.

[0066] The number of ultrafine bubbles immediately after generation (e.g., the number measured 15 minutes after generation) was 4.0 × 10⁻⁶ per milliliter. 7 More than one is acceptable, preferably 5.0 × 10⁻⁶. 7 More than one, preferably 8.0 × 10 7 More than one, preferably 1.0 × 10 8 More than one. By keeping the number of ultrafine bubbles within the above range, the liquid composition can contain ultrafine bubbles at a high concentration.

[0067] The bubbles constituting the ultrafine bubbles are preferably bubbles formed by the vaporization of liquefied gas at atmospheric pressure and 25°C. Therefore, in the liquid composition, the ultrafine bubbles are easily dispersed at a high concentration, and the effect based on the ultrafine bubbles can be easily obtained for a long period of time.

[0068] There are no particular restrictions on liquefied gases. As an example, liquefied gases include: lipophilic liquefied gases, such as liquefied petroleum gas composed of propane, n-butane, isobutane and mixtures thereof; hydrofluoroolefins with boiling points below 5°C, such as trans-1,3,3,3-tetrafluoroprop-1-ene and mixtures thereof; or amphiphilic liquefied gases composed of dimethyl ether and mixtures thereof, etc.

[0069] In cases where the liquefied gas contains liquefied petroleum gas composed of propane, n-butane, isobutane, and mixtures thereof, or hydrofluoroolefins with boiling points below 5°C such as trans-1,3,3,3-tetrafluoroprop-1-ene, and mixtures thereof (i.e., lipophilic liquefied gases), the ultrafine bubbles in the liquid composition easily adhere to the skin surface when applied to the human body, effectively removing sebum and other dirt from the application area over a long period. Furthermore, immersion in the liquid composition facilitates the adsorption and removal of oil and other cleaning effects. Moreover, when using a solvent containing water, the lipophilic liquefied gas easily separates from the liquid within the container or aerosol vessel that generates the ultrafine bubbles. However, the lipophilic liquefied gas is always saturated and dissolved in the liquid. Therefore, the liquid composition generates a large number of ultrafine bubbles that are also easily stabilized.

[0070] On the other hand, when the liquefied gas contains dimethyl ether, the liquid composition is more likely to obtain ultrafine bubbles with a particle size within a certain range, and the dispersion stability is better.

[0071] In addition to bubbles formed by the vaporization of liquefied gas, the ultrafine bubbles may also contain bubbles of compressed gas. For example, the amount of compressed gas dissolved in 1 mL of liquid (solvent) at 25°C and atmospheric pressure is preferably 0.001 mL or more, more preferably 0.005 mL or more. Furthermore, the amount of compressed gas dissolved is preferably 5 mL or less, more preferably 3 mL or less. By ensuring that the amount of compressed gas dissolved in the liquid is within the above-mentioned range, the ultrafine bubbles of compressed gas have small particle sizes, the size of the ultrafine particles is easily uniform, and they are easily dispersed at high concentrations.

[0072] More specifically, the compressed gases are nitrogen (0.0141 mL relative to 1 mL of water and 0.137 mL relative to 1 mL of ethanol), hydrogen (0.0175 mL relative to 1 mL of water and 0.0784 mL relative to 1 mL of ethanol), helium (0.0087 mL relative to 1 mL of water and 0.0294 mL relative to 1 mL of ethanol), sulfur hexafluoride (0.00545 mL relative to 1 mL of water), air (0.0167 mL relative to 1 mL of water), oxygen (0.0283 mL relative to 1 mL of water and 0.222 mL relative to 1 mL of ethanol), carbon dioxide (0.759 mL relative to 1 mL of water and 2.706 mL relative to 1 mL of ethanol), nitrous oxide (0.0588 mL relative to 1 mL of water), argon (0.0306 mL relative to 1 mL of water and 0.239 mL relative to 1 mL of ethanol), and mixtures thereof. When using compressed gases with low solubility (less than 1.0 mL relative to 1 mL of solvent), the liquid composition is more likely to produce small, ultrafine bubbles, and is therefore preferred.

[0073] (Other ingredients) In addition to the ultrafine bubbles described above, the liquid composition of this embodiment may also contain any ingredients such as various active ingredients, surfactants, thickeners, powders, etc.

[0074] The active ingredient can be appropriately selected according to the intended use or purpose of the liquid composition. For example, the active ingredient may include: various fragrances such as natural and synthetic fragrances; amphoteric resins such as (meth)acrylate dialkylaminoethyl ester•(meth)acrylate alkyl ester copolymer, vinyl acetate•crotonic acid copolymer, N-methacryloyloxyethyl N,N-dimethylammonium-α-N-methylcarboxylic acid betaine•alkyl methacrylate copolymer, octyl acrylate•hydroxypropyl acrylate•butylaminoethyl methacrylate copolymer; anionic resins such as acrylate alkanolamine, alkyl acrylate copolymer, alkyl acrylate copolymer emulsion, acrylic acid•acrylamide•ethyl acrylate copolymer, alkyl acrylate•methacrylic acid•silicone copolymer, octyl acrylate•acrylate copolymer, vinyl acetate•crotonic acid copolymer, crotonic acid•vinyl acetate•neodecanoate copolymer, and polyurethane; polyvinylpyrrolidone•N,N-dimethylaminoethyl ester methacrylate copolymer diethyl sulfate (polyquaternium-11), polyvinylpyrrolidone•N,N-dimethylaminoethyl ester methacrylate copolymer diethyl sulfate (polyquaternium-11), and polyvinylpyrrolidone•N,N-dimethylaminoethyl ester methacrylate copolymer diethyl sulfate (polyquaternium-11). Hair styling agents including ethyl methacrylate copolymer dimethyl sulfate, polyvinylpyrrolidone•N,N-dimethylaminoethyl methacrylate copolymer hydrochloride, dimethyl diallyl ammonium chloride•acrylamide copolymer (polyquaternium-7), and cationic resins such as chloro-o-[2-hydroxy-3-(trimethylamino)propyl]hydroxyethyl cellulose ether (polyquaternium-10); cooling agents such as l-menthol, camphor, and peppermint oil; retinol, retinol acetate, retinol palmitate, calcium pantothenate, and anti-corrosive agents. Vitamins including magnesium phosphate, sodium ascorbate, dl-α-tocopherol, tocopherol acetate, tocopherol, nicotinic tocopherol, thiamine dibenzoylcarbamate, riboflavin, and mixtures thereof; antioxidants including ascorbic acid, α-tocopherol, butylated hydroxytoluene, and butylated hydroxyanisole; amino acids including glycine, alanine, leucine, serine, tryptophan, cysteine, methionine, aspartic acid, glutamic acid, and arginine; and collagen, hyaluronic acid, and pyrrolidone carboxylic acid. Moisturizers such as carboxylic acid, sodium lactate, dl-pyrrolidone carboxylate, keratin, casein, lecithin, and urea; preservatives such as parabens, sodium benzoate, potassium sorbate, and phenoxyethanol; disinfectants such as benzalkonium chloride, benzyl chloride, chlorhexidine, and chloroformol; extracts such as royal jelly extract, peony extract, loofah extract, rose extract, lemon extract, aloe vera extract, calamus root extract, eucalyptus extract, sage extract, tea extract, seaweed extract, placenta extract, silk extract, Japanese swert extract, and carrot extract; aggregates such as zinc oxide, allantoin aluminum hydroxide, tannic acid, citric acid, and lactic acid; anti-inflammatory agents such as allantoin, glycyrrhetinic acid, dipotassium glycyrrhizate, and azulene; and hair growth agents such as minoxidil, adenosine, and glyceryl pentadecanoate.Deodorants include lauryl methacrylate, methyl benzoate, methyl phenylacetate, geraniol crotonate, acetophenone myristate, benzyl acetate, benzyl propionate, and green tea extract; UV absorbers include diethylaminohydroxybenzoyl benzoate, 2-ethylhexyl p-methoxycinnamate, ethylhexyl triazine, oxybenzone, hydroxybenzophenone sulfonic acid, sodium dihydroxybenzophenone sulfonate, and dihydroxybenzophenone; UV scattering agents include zinc oxide, titanium dioxide, and octyltrimethoxysilane-coated titanium dioxide; whitening agents include arbutin and kojic acid; antiperspirants include aluminum hydroxychloride and isopropyl methylphenol; and anti-inflammatory and analgesic agents include methyl salicylate, indomethacin, biphenylacetic acid, and ketoprofen.

[0075] When an active ingredient is included in the formulation, its content is not particularly limited. As an example, the content of the active ingredient in the liquid is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the content of the active ingredient in the liquid is preferably 20% by mass or less, more preferably 15% by mass or less. By keeping the content of the active ingredient within the above ranges, the effects based on the formulated active ingredient can be easily obtained.

[0076] Surfactants are appropriately proportioned to improve the cleaning effect of liquid compositions and the retention of ultrafine bubbles.

[0077] There are no particular limitations on surfactants. As an example, surfactants include nonionic surfactants such as cocamide DEA, polyoxyethylene alkyl ethers, polyglycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters; anionic surfactants such as fatty acid soaps, alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and sodium α-alkenyl sulfonate; cationic surfactants such as alkyl ammonium salts and polyoxyethylene alkylamines; amphoteric surfactants such as alkyl betaine, fatty acid amide propyl betaine, and alkylamine oxides; and silicone surfactants. In particular, by proportioning ionic surfactants, liquid compositions can easily achieve effects such as reducing the adhesion of positively or negatively charged pollen and other dispersible substances.

[0078] When a surfactant is included in the formulation, the amount of surfactant is not particularly limited. As an example, the surfactant content in the liquid is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. Furthermore, the surfactant content in the liquid is preferably 10% by mass or less, more preferably 8% by mass or less. By keeping the surfactant content within the above ranges, the effects of the surfactant formulation can be easily obtained.

[0079] Furthermore, in the presence of surfactants, if the liquid constituting the liquid composition is an aqueous solvent (such as water), micelles sometimes form where the oily components are emulsified. In this case, in addition to measuring the ultrafine bubbles, the particle size or number of micelles is also measured in the liquid composition, so it is sometimes impossible to accurately measure the particle size or number of ultrafine bubbles. In this case, in this embodiment, by measuring the particle size and number of the liquid composition before dispersing the ultrafine bubbles, and measuring the particle size and number of the liquid composition after dispersing the ultrafine bubbles, and then subtracting the number of particles with a particle size within a certain range, it is possible to estimate the particle size or number of ultrafine bubbles.

[0080] Thickeners are appropriately proportioned to increase the viscosity of liquid compositions or impart thixotropy, thereby slowing down the generation rate of ultrafine particles and adjusting the particle size of ultrafine particles to make ultrafine bubbles disperse more stably.

[0081] There are no particular restrictions on thickeners. For example, thickeners include cellulose-based polymers such as cellulose nanofibers, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and sodium carboxymethyl cellulose; gums such as xanthan gum, carrageenan, gum arabic, tragacanth, cationic guar gum, and gellan gum; water-soluble polymers such as (PEG-240 / decyltetradecyl polyether-20 / HDI) copolymers, polyurethane, dextran, sodium carboxymethyl dextran, dextrin, pectin, sodium alginate, sodium hyaluronate, and polyvinyl alcohol; cross-linked polyacrylic acid polymers such as carboxyethylene polymers; copolymers of acrylic acid and itaconic acid esters such as (acrylic acid / stearyl alcohol polyether itaconic acid) copolymers, (acrylic acid / cetyl alcohol polyether itaconic acid) copolymers, and (acrylic acid / amino acrylate / C10-30 alkyl PEG-20 itaconic acid) copolymers; and associative thickeners such as methyl vinyl ether maleic anhydride copolymers.

[0082] In cases where an associative thickener is present, a pH adjuster is preferably included. There are no particular limitations on the pH adjuster. As an example, a pH adjuster may include organic bases such as triethanolamine (TEA), 2-amino-2-methyl-1-propanol (AMP), diethanolamine (DEA), monoethanolamine (MEA), diisopropanolamine (DIPA), and 2-amino-2-methyl-1,3-propanediol (AMPD); inorganic bases such as potassium hydroxide, sodium hydroxide, and ammonium hydroxide; organic acids such as citric acid, glycolic acid, lactic acid, and phosphoric acid; and inorganic acids such as hydrochloric acid.

[0083] There is no particular limitation on the content of the thickener. As an example, the content of the thickener in the liquid is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the content of the thickener in the liquid is preferably 5% by mass or less, more preferably 3% by mass or less. By keeping the content of the thickener within the above range, it is easy to obtain the effect of adjusting the particle size of the ultrafine bubbles dispersed in the liquid composition, thereby achieving a more stable dispersion of the ultrafine bubbles.

[0084] Powder is used appropriately to allow ultrafine bubbles to adhere to the surface for better performance and to improve the user experience.

[0085] There are no particular restrictions on the powder. As an example, the powder could be talc, silica, zeolite, kaolin, mica, magnesium carbonate, calcium carbonate, zinc silicate, magnesium silicate, aluminum silicate, calcium silicate, etc.

[0086] When powder is included in the formulation, the powder content is not particularly limited. As an example, the powder content in the liquid is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. Furthermore, the powder content in the liquid is preferably 5% by mass or less, more preferably 3% by mass or less. By keeping the powder content within the above range, it is easy to obtain the effects based on the proportioned powder.

[0087] <Method for manufacturing liquid compositions and sprayed products> The method for manufacturing the liquid composition in this embodiment is not particularly limited. As an example, the liquid composition involves filling a pressurized, sealed container with a liquid as a stock solution, and filling the container with a liquefied gas, causing at least a portion of the liquefied gas to dissolve in the liquid. By opening the gas phase portion of the container to the atmosphere, the liquefied gas dissolved in the liquid is vaporized, thereby creating a liquid composition in which ultrafine bubbles are generated in the liquid and dispersed at a high concentration. Alternatively, the liquid composition involves filling a pressure-resistant container such as an aerosol container with a liquid as a stock solution, sealing the pressure-resistant container with a valve, and filling liquefied gas from the valve to produce a spray product. At least a portion of the liquefied gas dissolves in the liquid within the spray product, and by spraying it outwards, a liquid composition in which ultrafine bubbles are generated in the spray and dispersed at a high concentration is created. Hereinafter, as an example, a method for manufacturing a liquid composition containing ultrafine bubbles generated by the vaporization of liquefied gas using an aerosol product will be described.

[0088] Figure 1 This is a schematic cross-sectional view of an aerosol product 1 for manufacturing a liquid composition according to an embodiment of the present invention. Figure 1 The image shows aerosol product 1 in its non-use state. For example... Figure 1As shown, the aerosol product 1 of this embodiment mainly comprises a pressure-resistant container 2 filled with a contents consisting of a liquid L and a liquefied gas, a valve 3 installed in the pressure-resistant container 2, and a spraying member 4 installed in the valve 3 and having a spraying hole for spraying out the contents. The various structures will be described below. Furthermore, the structure of the aerosol product 1 is not limited to this embodiment. Therefore, the structure of the aerosol product 1 shown below is an example, and appropriate design changes can be made.

[0089] (Pressure vessel) The pressure vessel 2 is a container used to fill contents, namely liquid L, in a pressurized and sealed state. The pressure vessel 2 can be of a general shape. In this embodiment, the pressure vessel 2 is a bottomed cylindrical shape with an opening at the top. The opening is a filling port for filling liquid L. The pressure vessel 2 is fitted with a valve 3 at the opening for sealing. In addition, the pressure vessel 2 mainly has a container body for filling the aforementioned liquid L and liquefied gas.

[0090] •Pressure-resistant container 2 The pressure vessel 2 becomes an aerosol container by installing the valve 3 described below at the opening and then closing it.

[0091] There are no particular restrictions on the material of the pressure vessel 2. Examples of such materials include metals such as aluminum and tin-plated iron; synthetic resins such as polyethylene terephthalate and polyester; and pressure-resistant glass.

[0092] (Valve 3) Valve 3 is a component installed in the opening of pressure vessel 2 and used to seal the interior of pressure vessel 2. It has a valve mechanism 31 that can switch the connection / cut-off between the interior and exterior of pressure vessel 2 by moving up and down, and a housing 32 that forms a defined internal space to accommodate valve mechanism 31. Valve mechanism 31 includes: valve stem 33 with a valve stem hole 33a that communicates with the exterior by pressing downward; valve stem rubber 34 that seals valve stem hole 33a; and spring 35 that always applies force to valve stem 33 from below vertically upward. A liquid phase inlet hole 32a is formed in the lower part of housing 32, which communicates the interior space of housing 32 with the interior of pressure vessel 2 via pipe 36. If valve stem hole 33a is opened by the action of valve 3, the liquid L filled in pressure vessel 2 is drawn into housing 32 through liquid phase inlet hole 32a from the opening at the lower end of pipe 36 by the pressure of liquefied gas, passes through the passage in valve stem hole 33a and valve stem 33, and is sent to ejection component 4.

[0093] There are no particular limitations on the method of filling the pressure vessel 2 with liquid L and liquefied gas. As an example, liquid L is filled from the opening of the pressure vessel 2, and valve 3 is fixed at the opening of the pressure vessel 2. Liquefied gas is then filled from the valve stem 33 of valve 3, so that a portion of the liquefied gas dissolves in liquid L.

[0094] The liquefied gas is filled into the pressure vessel 2. A portion of the liquefied gas dissolves in the liquid L, but it also exists in the gas phase. When the liquefied gas is filled to a level exceeding the saturation dissolution amount in the liquid L, the liquefied gas separates from the liquid L, forming a liquid phase La. At the moment of filling the pressure vessel 2, the amount of liquefied gas dissolved relative to 1 mL of liquid L, when converted to liquid, is preferably 0.0001 mL or more, more preferably 0.0003 mL or more. Furthermore, the amount of liquefied gas dissolved is preferably 0.5 mL or less, more preferably 0.3 mL or less. By keeping the amount of liquefied gas dissolved within the above range, the liquid composition readily generates a large number of ultrafine bubbles after being ejected. In this embodiment, the amount of liquefied gas dissolved refers to the amount of liquefied gas dissolved in liquid L at 25°C.

[0095] More specifically, the liquefied gas is liquefied petroleum gas of propane (0.014 mL relative to 1 m water), butane (0.010 mL relative to 1 m water) and mixtures thereof, trans-1,3,3,3-tetrafluoroprop-1-ene (0.000319 mL relative to 1 m water), dimethyl ether (0.106 mL relative to 1 m water) and mixtures thereof, etc.

[0096] The pressure inside the aerosol container after filling with liquefied gas and dissolving it in liquid L is 0.1 to 1.0 MPa (gauge pressure) at 25°C, preferably 0.15 to 0.8 MPa (gauge pressure). This pressure can be adjusted by filling with the above-mentioned amount of dissolved gas as the vaporized liquefied gas.

[0097] (Ejection component 4) The ejection component 4 is used to eject liquid L containing liquefied gas collected through valve 3 by operating valve 3. The ejection component 4 mainly consists of an operating part 5 that is operated by the user. Figure 1 As shown, the ejector component 4 is installed on the valve stem 33 of the valve 3.

[0098] • Operations Section 5 The operating part 5 is a generally cylindrical portion, having one end with a mounting hole 51 for mounting the valve stem 33 and the other end with a spray hole 52 for discharging contents. The mounting hole 51 is a cylindrical connection port formed at one end of the operating part 5, into which the valve stem 33 is inserted. An internal passage for contents removed from the valve 3 to pass through is opened at the bottom of the mounting hole 51. The other end of the internal passage opens as the spray hole 52.

[0099] The internal passage is a series of passages (ejection passages) through which the contents received from valve 3 pass to the ejection port 52. A generally L-shaped first conduit 53 is formed within the internal passage for the contents received from valve 3 to pass through. A generally cylindrical branch member 54, which branches the flow path by causing the contents passing through the first conduit 53 to collide and change the flow direction, and a nozzle 55 covering the circumferential surface of the branch member 54 are installed within the space of the first conduit 53. Furthermore, 2 to 10 grooves (not shown) are formed at the downstream end of the first conduit 53, diffusing outwards from the first conduit 53. Therefore, by inserting the branch member 54 into the cylindrical space, a diffusion passage for the contents to flow outwards is formed between the grooves and the branch member 54.

[0100] The nozzle 55 is a bottomed cylindrical shape, consisting of a generally disc-shaped bottom and a peripheral portion covering the circumferential surface of the branch member 54. Multiple grooves (not shown) are formed at the bottom of the nozzle 55, which allow contents passing between the outer peripheral surface of the branch member 54 and the inner peripheral surface of the peripheral portion to flow from the outer periphery toward the centrally formed ejection hole 52. Furthermore, at the bottom of the nozzle 55, a vortex chamber for swirling the contents is formed at the convergence point of 2 to 10 grooves. By installing the nozzle 55 on the branch member 54, a converging passage for the contents to flow from the grooves and the branch member 54 into the vortex chamber is formed. An ejection hole 52 is provided at the center of the vortex chamber. In addition, multiple transverse grooves (not shown) are formed on the outer peripheral surface of the branch member 54 for allowing contents from the diffusion passage branching outwards on the first conduit 53 side to flow into the converging passage at the bottom of the nozzle 55. These transverse grooves can be spiral-shaped to lengthen the flow path and increase the passage resistance to further slow the flow velocity.

[0101] The contents, drawn in from valve 3 and passing through the first conduit 53, collide with the branch member 54, causing the flow direction to change radially through the diffusion path. Next, the contents pass through the transverse groove between the outer circumferential surface of the branch member 54 and the inner circumferential surface of the nozzle 55, causing the flow direction to change centrally through the converging path. The contents are then guided into the vortex chamber, where they become a vortex and are ejected from the ejection port 52.

[0102] There is no particular limitation on the inner diameter of the first conduit 53. The inner diameter of the first conduit 53 can be adjusted appropriately according to the desired injection speed, etc. As an example, the inner diameter of the first conduit 53 is 0.5 to 3 mm.

[0103] Furthermore, there is no particular limitation on the diameter of the nozzle 52. The cross-sectional area (diameter) of the nozzle 52 is appropriately adjusted according to the desired jet velocity, etc. As an example, the diameter of the nozzle 52 is 0.2 to 0.6 mm. There is no particular limitation on the cross-sectional shape of the nozzle 52. As an example, the cross-sectional shape of the nozzle 52 is circular, rectangular, etc., and there can be multiple nozzles.

[0104] exist Figure 1 In the ejector component 4 shown, which has diffusion and convergence channels, the contents received from valve 3 and passing through the first pipe 53 are subject to channel resistance as they flow through each channel, suppressing the vaporization rate of the dissolved gas. When the contents are ejected from the ejector orifice, the ejection force weakens (the ejection pressure decreases), but the particles are small and diffuse over a wide area, making it easy for the dissolved gas to vaporize immediately. As a result, the particle size of the generated ultrafine bubbles becomes smaller, and the number of bubbles increases.

[0105] Figure 2 This is a schematic diagram illustrating one embodiment of the ejection member 6 used to manufacture an aerosol product of the liquid composition of this embodiment.

[0106] Figure 2 The ejector component 6 shown has an integrally formed operating part 6a with a branching member 62, and a nozzle 7 is mounted thereon. In the ejector component 6 with such a converging passage, from the valve 3 (see reference...) Figure 1 The contents of the first conduit 61 pass through the gap between the outer peripheral surface of the branch member 62 and the inner peripheral surface of the nozzle 7. The flow direction is changed to a central direction by the converging passage, and the contents are guided into the vortex chamber R to form a vortex, and then ejected from the ejection hole 7p. The number of grooves in the converging passage is preferably 2 to 10, more preferably 3 to 8.

[0107] Figure 2 The operating part 6a of the ejection member 6 has an internal passage (first pipe 61) that is approximately L-shaped and a fitting part 63 for inserting the nozzle 7. The fitting part 63 is a generally cylindrical recess. A cylindrical protrusion (cylindrical part 64) is provided on the inner bottom surface of the fitting part 63.

[0108] The cylindrical portion 64 is the part embedded within the foot 71 of the nozzle 7 when the nozzle 7 is installed onto the operating part 6a. In the state where the nozzle 7 is installed (i.e.... Figure 2 In the state of (the point where), the side circumferential surface of the cylindrical portion 64 is slightly separated from the inner circumferential surface of the foot portion 71. The gap and internal passage (first conduit 61) formed by this separation of the cylindrical portion 64 and the foot portion 71 constitute the internal passage 74 of the ejection member, through which the contents collected from the aerosol container pass during ejection. Furthermore, as Figure 2 As shown, the front end face of the cylindrical part 64 abuts against the inner bottom surface of the nozzle 7.

[0109] The nozzle 7 is a bottomed cylindrical shape, consisting of a base plate 72 and cylindrical feet 71 erected around one surface of the base plate 72. The base plate 72 is a disc-shaped portion with a specified thickness, forming a recess 73 and a groove connecting to the recess 73. An ejection hole 7p for communication with the outside is formed at the center of the inner bottom surface of the recess.

[0110] By mounting the nozzle 7 to the operating part 6a, the opening surface of the aforementioned recess abuts against the front end face of the cylindrical part 64 and is thus closed. Consequently, the ejection member 6 forms a vortex chamber R defined by the recess and the front end face of the cylindrical part 64. The size of the vortex chamber R is not particularly limited. As an example, the vortex chamber R is a cylindrical space with a diameter of 0.8 to 2.0 mm, preferably 1.0 to 1.5 mm, and a height (depth) of approximately 0.05 to 0.2 mm. Furthermore, the shape of the vortex chamber R is not limited to a cylindrical shape. The vortex chamber R can be any shape with an inner circumference that allows the introduced contents to swirl.

[0111] Similarly, the opening of the slot is closed by mounting the nozzle 7 to the operating part 6a and abutting against the front end face of the cylindrical part 64. Thus, the ejection member 6 forms a slot that connects to the vortex chamber R.

[0112] The vortex chamber R is a roughly cylindrical space with grooves connected around it. The grooves are passages connecting the internal passage of the ejection component to the vortex chamber R, forming a side opening at one end connected to the internal passage of the ejection component and a side opening at the other end connected to the vortex chamber R.

[0113] The slots are arranged radially at approximately equal intervals relative to the swirl chamber R. Each slot is formed to guide the contents along the inner periphery of the swirl chamber R. By forming the slots in this direction, the contents introduced into the swirl chamber R through the slots do not directly face the ejection port 7p, but instead swirl within the swirl chamber R along its inner periphery. After swirling within the swirl chamber R, the contents are ejected from the ejection port 7p located at the center of the swirl chamber R.

[0114] The size of the ejection orifice 7p is not particularly limited. As an example, the diameter of the ejection orifice 7p is preferably about 0.1 to 0.8 mm, more preferably about 0.2 to 0.6 mm. With an ejection orifice 7p of this size, since the contents are ejected in a wide-range diffusion manner after sufficient swirling in the vortex chamber R, the ejected particle size itself becomes smaller, the dissolved liquefied gas is easily vaporized, and many ultrafine bubbles are easily generated. Therefore, the particle size D90, where the volumetric accumulation distribution of ultrafine bubbles in the liquid composition is 90%, tends to be smaller. Furthermore, ultrafine bubbles are easily dispersed at a high concentration.

[0115] Figure 3 This is a schematic diagram illustrating one embodiment of the ejection member 8 used for manufacturing an aerosol product of a liquid composition according to one embodiment of the present invention.

[0116] like Figure 3 As shown, the ejector component 8 has no branch components and is equipped with a nozzle 9 that is linearly connected to the first conduit 81 and the ejector hole 91. In this ejector component 8, the nozzle 9 is connected to the first conduit 81 in a straight line. (Refer to...) Figure 1The contents that have been collected and passed through the first conduit 81 are ejected from the ejector hole 91 at a high jet pressure, which can powerfully impart the liquid composition containing ultrafine bubbles to the object.

[0117] The nozzle 9 protrudes outward and is generally cylindrical. The inner diameter of the passage within the nozzle 9, from the root 92 to the ejection hole 91, is approximately the same. The ejection hole 91 may be the same as or smaller than the inner diameter. The inner diameter of the ejection hole 91 is preferably, for example, 0.3 to 1.5 mm, more preferably 0.5 to 1.3 mm. Therefore, the contents ejected using the ejection member 8 flow linearly within the passage of the nozzle 9 and are ejected to the outside from the ejection hole 91.

[0118] Furthermore, when it is necessary to apply passage resistance to the contents flowing within the nozzle to suppress the vaporization of dissolved liquefied gas, and to generate ultrafine bubbles at a high concentration when ejected to the outside, the size of the nozzle 9, for example, the inner diameter, is preferably 0.3 to 2.5 mm, more preferably 0.5 to 2.0 mm. Additionally, the length of the nozzle 9 is preferably 3 to 15 mm, more preferably 5 to 12 mm.

[0119] Returning to the overall description of aerosol product 1, as follows, in this embodiment, after the liquid L containing dissolved liquefied gas is taken out from valve 3, it is appropriately slowed down during its passage through the spray passage and sprayed out from the spray hole 52 in the form of ultrafine bubbles generated along with the vaporization of the dissolved liquefied gas, thus constituting a liquid composition.

[0120] The above description pertains to one embodiment of the present invention. Specifically, in the above embodiment, a method and liquid composition are illustrated for manufacturing a liquid composition by filling an aerosol product with a liquid as a stock solution, dissolving a portion of the liquefied gas in the liquid and spraying it out, thereby dispersing ultrafine bubbles of the liquefied gas in the liquid.

[0121] Furthermore, the liquid composition can be used to fill a dispensing container as a dispensing product, where the liquid composition is manufactured in a pressurized, sealed tank. Examples of such a dispensing container include... Figure 1 From the viewpoint of enabling the stable dispersion of ultrafine bubbles, containers that can be filled with liquid compositions in a liquid-tight state are preferred, including aerosol containers, double-layered aerosol containers with an inner bag containing a liquid-filled composition inside the container body, pump containers with a direct-pressure pump or a accumulator pump in the container body, pump containers with an inner bag containing a liquid bag inside the container body and having a double-layered structure without an air pump, and small packages.

[0122] [Second Implementation] In one embodiment (the second embodiment) of the present invention, the liquid composition preferably uses ultrafine bubbles as compressed gas bubbles. Furthermore, in the following description, for structures identical to those described in the first embodiment, the disclosure in the first embodiment is referenced and appropriately omitted.

[0123] (liquid) The liquid constituting the liquid composition has the same structure as that described in the first embodiment.

[0124] The solvent content is preferably 60% by mass or more in the liquid, more preferably 70% by mass or more. Furthermore, the solvent content is preferably 100% by mass or less in the liquid, more preferably 99.9% by mass or less. By keeping the solvent content within the above range, the ultrafine bubbles of the compressed gas described above have small particle sizes and are easily and stably dispersed over a long period. In particular, when the liquid contains 60% by mass or more of water, the ultrafine bubbles in the liquid composition have small particle sizes and a narrow particle size distribution width, resulting in uniform ultrafine particle size and a sustained stabilizing effect. Furthermore, the components exemplified in aqueous or oil-based solvents can also be added to the solvent as additives or active ingredients.

[0125] (Ultra-fine bubbles) Ultrafine bubbles are tiny bubbles dispersed in a liquid.

[0126] The particle size D90, with a volumetric cumulative distribution value of 90% for the ultrafine bubbles, is the same as that described in the first embodiment. By keeping D90 within the aforementioned range, the liquid composition contains a majority of tiny bubbles with an average particle size of nanometers (1–1000 nm), particularly ultrafine bubbles of 10–300 nm. As a result, the obtained liquid composition exhibits high transparency, and the ultrafine bubbles can be dispersed at a high concentration and stably over a long period. Furthermore, since the ultrafine bubbles have increased opportunities to come into contact with the target object, it is easier to obtain the effect of adsorbing effective components onto the ultrafine bubbles, thereby inhibiting the adhesion of dirt components and purifying the object by adsorbing dirt components.

[0127] Furthermore, in this embodiment, the method for measuring the particle size D90, which has a cumulative distribution value of 90%, is the same as that described in the first embodiment.

[0128] According to the aforementioned nano-tracking particle size measuring device, in addition to D90, it can also measure particle size D50 with a cumulative distribution value of 50% and particle size D10 with a cumulative distribution value of 10%. Furthermore, the nano-tracking particle size measuring device can also measure the number of ultrafine bubbles per milliliter.

[0129] The D50 of the ultrafine bubbles is preferably 30 nm or more, more preferably 50 nm or more. Furthermore, the D50 of the ultrafine bubbles is preferably 200 nm or less, more preferably 170 nm or less. Furthermore, the D10 of the ultrafine bubbles is preferably 10 nm or more, more preferably 20 nm or more. Furthermore, the D10 of the ultrafine bubbles is preferably 150 nm or less, more preferably 100 nm or less. By keeping the D50 and D10 within the above ranges, in the liquid composition, among the tiny bubbles with an average particle size of nanometers (1–1000 nm), particularly ultrafine bubbles of 10–300 nm constitute the majority. As a result, the obtained liquid composition has high transparency, and the ultrafine bubbles can be dispersed at a high concentration and stably for a long period.

[0130] In the ultrafine bubbles of this embodiment, the proportion of bubbles with a particle size exceeding 300 nm is preferably 10% or less, and more preferably 5% or less, in the total number of bubbles.

[0131] The number of ultrafine bubbles immediately after generation (e.g., 15 minutes after generation) is 4.0 × 10⁻⁶ per milliliter. 7 More than one is acceptable, preferably 4.5 × 10⁻⁶. 7 More than one, preferably 8.0 × 10 7 More than one. By keeping the number of ultrafine bubbles within the above range, the liquid composition can contain ultrafine bubbles at a high concentration.

[0132] The bubbles constituting the ultrafine bubbles are preferably bubbles formed by the vaporization of compressed gas dissolved in a liquid under pressure through decompression. Therefore, the ultrafine bubbles in the liquid composition have small particle sizes, the ultrafine particles are easily uniform in size, they are easily dispersed at high concentrations, and the effects based on ultrafine bubbles can be easily obtained over a long period.

[0133] There are no particular limitations on the compressed gas. As an example, at 25°C and atmospheric pressure, the solubility of the compressed gas relative to 1 mL of liquid (solvent) is preferably 0.001 mL or more, more preferably 0.005 mL or more. Furthermore, the solubility of the compressed gas relative to the liquid is preferably 5 mL or less, more preferably 3 mL or less. By ensuring that the solubility of the compressed gas in the liquid is within the above range, the particle size of the ultrafine bubbles is small, the size of the ultrafine particles is easily uniform, and they are easily dispersed at high concentrations.

[0134] More specifically, the compressed gases are nitrogen (0.0141 mL relative to 1 mL of water and 0.137 mL relative to 1 mL of ethanol), hydrogen (0.0175 mL relative to 1 mL of water and 0.0784 mL relative to 1 mL of ethanol), helium (0.0087 mL relative to 1 mL of water and 0.0294 mL relative to 1 mL of ethanol), sulfur hexafluoride (0.00545 mL relative to 1 mL of water), air (0.0167 mL relative to 1 mL of water), oxygen (0.0283 mL relative to 1 mL of water and 0.222 mL relative to 1 mL of ethanol), carbon dioxide (0.759 mL relative to 1 mL of water and 2.706 mL relative to 1 mL of ethanol), nitrous oxide (0.0588 mL relative to 1 mL of water), argon (0.0306 mL relative to 1 mL of water and 0.239 mL relative to 1 mL of ethanol), and mixtures thereof. When using a compressed gas with low solubility of less than 1.0 mL relative to 1 mL of solvent, the content of smaller ultrafine bubbles in the liquid composition tends to increase, which is therefore preferable.

[0135] (Other ingredients) In addition to the ultrafine bubbles described above, the liquid composition of this embodiment may also contain any components such as various active ingredients, surfactants, thickeners, powders, etc. Examples of these components are the same as those described in the first embodiment.

[0136] When an active ingredient is included in the formulation, the content of the active ingredient is not particularly limited. As an example, the content of the active ingredient in the liquid is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the content of the active ingredient in the liquid is preferably 20% by mass or less, more preferably 15% by mass or less. By keeping the content of the active ingredient within the above range, it is easy to obtain the effect based on the formulation of the active ingredient.

[0137] Surfactants are appropriately formulated to improve cleaning effectiveness and enhance the retention of ultrafine bubbles by allowing them to adsorb dirt components.

[0138] When a surfactant is included in the formulation, the amount of surfactant is not particularly limited. As an example, the surfactant content in the liquid is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the surfactant content in the liquid is preferably 10% by mass or less, more preferably 8% by mass or less. By keeping the surfactant content within the above ranges, the effects of the surfactant formulation can be easily obtained.

[0139] Furthermore, in the presence of surfactants, if the liquid constituting the liquid composition is an aqueous solvent (such as water), micelles sometimes form where the oily components are emulsified. In this case, in addition to measuring the ultrafine bubbles, the particle size or number of micelles is also measured in the liquid composition, so it is sometimes impossible to accurately measure the particle size or number of ultrafine bubbles. In this case, in this embodiment, by measuring the particle size and number of particles in the liquid before dispersing the ultrafine bubbles, and measuring the particle size and number of particles in the liquid composition after dispersing the ultrafine bubbles, and then subtracting the number of particles within a certain particle size range, it is possible to estimate the particle size and number of ultrafine bubbles.

[0140] Thickeners are appropriately proportioned to increase the viscosity of liquid compositions or impart thixotropy, thereby slowing down the generation rate of ultrafine particles and adjusting the particle size of ultrafine particles to make ultrafine bubbles disperse more stably.

[0141] There is no particular limitation on the content of the thickener. As an example, the content of the thickener in the liquid is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the content of the thickener in the liquid is preferably 5% by mass or less, more preferably 3% by mass or less. By keeping the content of the thickener within the above range, it is easy to obtain an effect that allows for adjustment of the particle size of the ultrafine bubbles dispersed in the liquid composition, resulting in a more stable dispersion of the ultrafine bubbles.

[0142] Powder is used appropriately to allow ultrafine bubbles to adhere to the surface for better performance and to improve the user experience.

[0143] When powder is included in the formulation, the powder content is not particularly limited. As an example, the powder content in the liquid is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. Furthermore, the powder content in the liquid is preferably 5% by mass or less, more preferably 3% by mass or less. By keeping the powder content within the above range, it is easy to obtain the effects based on the proportioned powder.

[0144] <Method for manufacturing liquid compositions and sprayed products> The method for manufacturing the liquid composition in this embodiment is not particularly limited. As an example, the liquid composition is prepared by adding an active ingredient or the like to a solvent, and this liquid is used as a stock solution to fill a pressurized, sealed container. Compressed gas is then added to the container, increasing the pressure inside, causing at least a portion of the compressed gas to dissolve in the liquid. By opening the gas phase portion of the container to the atmosphere, the compressed gas dissolved in the liquid is vaporized, thereby enabling the production of a liquid composition that generates ultrafine bubbles and is dispersed at a high concentration within the liquid.

[0145] Furthermore, the liquid composition involves filling a pressure-resistant container, such as an aerosol container, with a valve installed to seal the pressure-resistant container, and filling it with compressed gas to produce an ejected product. At least a portion of the compressed gas dissolves in the liquid within the ejected product, and by ejecting it to the outside, a liquid composition that generates ultrafine bubbles and disperses at a high concentration within the ejected material can be produced.

[0146] Furthermore, during liquid preparation, bubbles of various sizes are dispersed within the liquid. However, by pressurizing the liquid, these bubbles are compressed and subsequently dissolved. As a result, large bubbles disappear. If the pressure is reduced from this state, the compressed gas dissolved in the liquid vaporizes into ultrafine bubbles. Consequently, the size of these ultrafine bubbles tends to be uniform.

[0147] The following description, as an example, illustrates a method for manufacturing a liquid composition containing ultrafine bubbles of compressed gas using an aerosol product. Furthermore, structures identical to those described in the first embodiment will be labeled with the same names and reference numerals, and descriptions will be omitted where appropriate.

[0148] Figure 14 This is a schematic cross-sectional view of an aerosol product 1 for manufacturing a liquid composition according to an embodiment of the present invention. Figure 14 The image shows aerosol product 1 in its non-use state. For example... Figure 14 As shown, the aerosol product 1 of this embodiment mainly includes: a pressure-resistant container 2 filled with contents consisting of liquid L and compressed gas; a valve 3 installed in the pressure-resistant container 2; and a spray member 4 installed in the valve 3 and having a spray hole for spraying out the contents. The various structures will be described below. Furthermore, the structure of the aerosol product 1 is not limited to this embodiment. Therefore, the structure of the aerosol product 1 shown below is illustrative and can be appropriately modified.

[0149] (Pressure vessel) The pressure container 2 is a container used to fill contents, namely liquid L, in a pressurized and sealed state. The pressure container 2 can be of a general shape. In this embodiment, the pressure container 2 is a bottomed cylindrical shape with an opening at the top. The opening is a filling port for filling liquid L. The pressure container 2 is fitted with a valve 3 at the opening for sealing. In addition, the pressure container 2 mainly has a container body for filling the aforementioned liquid L and compressed gas.

[0150] •Pressure-resistant container 2 The pressure container 2 becomes an aerosol container by installing the valve 3 described below at the opening and closing it. The pressure container 2 has a bottomed cylindrical outer container 21 and an inner bag 22 inside the outer container 21.

[0151] There are no particular restrictions on the material of the outer container 21. Examples of such materials include metals such as aluminum and tin-plated iron; synthetic resins such as polyethylene terephthalate and polyester; and pressure-resistant glass.

[0152] The inner bag 22 is disposed inside the outer container 21 and is a bag-shaped container that can be compressed by the pressure of compressed gas. The inner bag 22 is filled with the aforementioned liquid L in a liquid-tight state. The material of the inner bag 22 is not particularly limited. As an example, the material of the inner bag 22 may be polyolefins such as polyethylene, ethylene-vinyl alcohol copolymers, polyamides, and other synthetic resins. In addition, the inner bag 22 may be a single layer of the aforementioned synthetic resin or a laminate of multiple layers.

[0153] (Valve 3) Valve 3 is a component installed at the opening of pressure vessel 2 and used to seal the interior of pressure vessel 2. It includes: a valve mechanism 31 capable of switching communication / cut-off between the interior of inner bag 22 and the outside by moving up and down; and a housing 32 forming a defined internal space for accommodating valve mechanism 31. Valve mechanism 31 includes: a valve stem 33 having a valve stem hole 33a that communicates with the outside by pressing downward; a valve stem rubber 34 sealing valve stem hole 33a; and a spring 35 that always applies force to valve stem 33 from below vertically upward. A receiving hole 32a is formed on the side peripheral wall of housing 32, communicating between the interior space of housing 32 and the interior of pressure vessel 2 (inner bag 22). When the valve stem hole 33a is opened by the action of the valve 3, the liquid L in the inner bag 22 is pressed by the pressure of the compressed gas filling the space between the outer container 21 and the inner bag 22, and is drawn into the housing 32 from the inlet hole 32a. It then passes through the passage in the valve stem hole 33a and the valve stem 33 and is sent to the ejection component 4.

[0154] Furthermore, the location of the inlet 32a is not limited to the side wall of the housing 32. The inlet 32a may also be located at the lower part of the housing 32. In this embodiment, since the liquid L is filled in the inner bag 22 in a liquid-tight state, it can be ejected regardless of the orientation of the pressure container 2.

[0155] In addition, such as Figure 14 As shown, the inner bag 22 of this embodiment is liquid-tightly filled with liquid L. Furthermore, if liquid L is ejected and consumed, the inner bag 22 contracts under the pressure of compressed gas, thus maintaining the liquid-tight state of the inner bag 22. As a result, the inlet hole 32a is always open in the liquid L, but not in the gas phase portion. Consequently, the aerosol product 1 does not eject the gas phase portion or compressed gas when ejected, making it easy to adjust the particle size D90 of the obtained ultrafine bubbles to the range of 50–300 nm. Moreover, even when vibrations are applied during transportation, the liquid L inside the inner bag remains almost stationary. Therefore, it is possible to stably manufacture a liquid composition that disperses ultrafine bubbles when ejected externally.

[0156] Furthermore, as a variation of the aerosol product 1 of this embodiment, in the case where the inner bag 22 is not provided, and liquid is filled in such a way that it occupies a portion of the internal volume of the container body to form a gas phase portion and a liquid phase portion within the container body, it is preferable that the transverse hole (gas phase inlet hole) of the shell is closed. In this case, by providing a liquid phase inlet hole at the bottom of the shell and installing a long strip suction tube that is inserted through the liquid phase inlet hole, it is possible to draw only the liquid constituting the liquid phase portion into the shell, thereby preventing the gas phase portion from being drawn in. Even in this case, since the aerosol product does not eject the gas phase portion when it is sprayed, it is easy to adjust the particle size D90 of the obtained ultrafine bubbles to the range of 50 to 300 nm.

[0157] There are no particular limitations on the method of filling the pressure container 2 with liquid L and compressed gas. As an example, the method involves filling the inner bag 22 with liquid L through the opening, inserting and closing the valve 3 into the opening of the inner bag 22, then filling the space between the outer container 21 and the inner bag 22 with compressed gas, fixing the valve 3 to the pressure container 2, and allowing a portion of the vaporized compressed gas to permeate through the inner bag 22 and dissolve saturatedly in the liquid L. In this case, the inner bag 22 is preferably a single layer of a breathable synthetic resin (e.g., polyethylene).

[0158] Compressed gas is filled into the gap between the outer container 21 and the inner bag 22 of the pressure-resistant container 2. A portion of the compressed gas dissolves in the liquid through the inner bag 22 over time. The compressed gas located in the gap between the outer container 21 and the inner bag 22 acts as a pressurizing agent to pressurize the inner bag 22, allowing it to be ejected. The amount of compressed gas dissolved relative to 1 mL of liquid L in the inner bag 22 at the moment of saturation in the pressure-resistant container 2 should be 30 ppm or more, preferably 40 ppm or more. Furthermore, the amount of compressed gas dissolved is preferably 80,000 ppm or less, more preferably 70,000 ppm or less. By keeping the amount of compressed gas dissolved within the above range, a large number of ultrafine bubbles are easily generated after ejection. In this embodiment, the amount of compressed gas dissolved is a value calculated based on the volume of liquid filled into the pressure-resistant container, the volume of the gas phase portion of the compressed gas, the amount of compressed gas filled, and the pressure at which the compressed gas reaches equilibrium when dissolved in the liquid within the pressure-resistant container at 25°C.

[0159] The pressure inside the pressure vessel 2, filled with compressed gas and saturated dissolved in liquid L, is 0.3–1.0 MPa (gauge pressure) at 25°C, preferably 0.4–0.9 MPa (gauge pressure). By adjusting to this pressure, even if the pressure inside the pressure vessel decreases due to the reduction of liquid volume caused by ejection, the compressed gas remains in the liquid within the aforementioned dissolved amount range, making it easy to obtain a liquid composition in which ultrafine bubbles are stably dispersed at a high concentration over a long period.

[0160] (Ejection component 4) The ejection component 4 is used to eject liquid L containing compressed gas drawn in through valve 3 by operating valve 3. The ejection component 4 is mainly composed of the user-operated operating part 5. Figure 14 As shown, the ejector component 4 is installed on the valve stem 33 of the valve 3.

[0161] • Operations Section 5 The operating part 5 is a generally cylindrical portion, having one end with a mounting hole 51 for mounting the valve stem 33 and the other end with a spray hole 52 for discharging contents. The mounting hole 51 is a cylindrical connection port formed at one end of the operating part 5, into which the valve stem 33 is inserted. An internal passage for contents removed from the valve 3 to pass through is opened at the bottom of the mounting hole 51. The other end of the internal passage opens as the spray hole 52.

[0162] The internal passage is a series of passages (ejection passages) through which the contents received from valve 3 pass to the ejection port 52. A generally L-shaped first conduit 53 is formed within the internal passage for the contents received from valve 3 to pass through. A generally cylindrical branch member 54, which branches the flow path by causing the contents passing through the first conduit 53 to collide and change its flow direction, is installed in the space of the first conduit 53, along with a nozzle 55 covering the circumferential surface of the branch member 54. Furthermore, 2 to 10 grooves (not shown) are formed at the downstream end of the first conduit 53, diffusing outwards from the first conduit 53. Therefore, by inserting the branch member 54 into the cylindrical space, a diffusion passage is formed between the grooves and the branch member 54, allowing the contents to flow outwards.

[0163] The nozzle 55 is a bottomed cylindrical shape, consisting of a generally disc-shaped bottom and a peripheral portion covering the circumferential surface of the branch member 54. Two to ten, preferably two to eight, grooves (not shown) are formed at the bottom of the nozzle 55. These grooves allow contents passing between the outer peripheral surface of the branch member 54 and the inner peripheral surface of the peripheral portion to flow from the outer periphery toward the centrally formed ejection hole 52. Furthermore, a vortex chamber for swirling the contents is formed at the confluence of these grooves. By installing the nozzle 55 on the branch member 54, a converging passage is formed between the grooves and the branch member 54, allowing the contents to flow into the vortex chamber. An ejection hole 52 is provided at the center of the vortex chamber. In addition, multiple transverse grooves (not shown) are formed on the outer peripheral surface of the branch member 54 to allow contents from the diffusion passage branching outwards on the first conduit 53 side to flow into the converging passage at the bottom of the nozzle 55. The transverse grooves can be spiral-shaped to lengthen the flow path and increase the passage resistance to further slow the flow velocity.

[0164] The contents, drawn in from valve 3 and passing through the first pipe 53, collide with the branch member 54, and are diverted by the diffusion passage to flow radially. Next, passing through the transverse groove between the outer circumferential surface of the branch member 54 and the inner circumferential surface of the nozzle 55, the contents are diverted by the converging passage to flow centrally. The contents are then guided into the vortex chamber, where they become a vortex and are ejected from the ejection port 52.

[0165] There is no particular limitation on the inner diameter of the first conduit 53. The inner diameter of the first conduit 53 can be adjusted appropriately according to the desired injection speed, etc. As an example, the inner diameter of the first conduit 53 is 0.5 to 3 mm.

[0166] Furthermore, there is no particular limitation on the diameter of the nozzle 52. The cross-sectional area (diameter) of the nozzle 52 is appropriately adjusted according to the desired jet velocity, etc. As an example, the diameter of the nozzle 52 is 0.2 to 0.6 mm. There is no particular limitation on the cross-sectional shape of the nozzle 52. As an example, the cross-sectional shape of the nozzle 52 is circular, rectangular, etc., and there can be multiple nozzles.

[0167] exist Figure 14 In the ejector component 4 shown, which has diffusion and convergence channels, the contents received from the valve 3 and passing through the first pipe 53 are subject to channel resistance as they flow through each channel, and the vaporization rate of the gas dissolved in the liquid is suppressed. When the contents are ejected from the ejector hole to the outside, the particles of the ejected material become smaller, the particle size of the generated ultrafine bubbles becomes smaller, and the number of bubbles generated also increases.

[0168] Figure 15 This is a schematic diagram illustrating one embodiment of the ejection member 6 used to manufacture an aerosol product of the liquid composition of this embodiment.

[0169] Figure 15 The ejector component 6 shown has an integrally formed operating part 6a with a branching member 62, and a nozzle 7 is mounted thereon. In the ejector component 6 with such a converging passage, from the valve 3 (see reference...) Figure 14 The contents that have been drawn into and passed through the first conduit 61 pass through the gap between the outer peripheral surface of the branch member 62 and the inner peripheral surface of the nozzle 7. The flow direction is changed to a central direction by the converging passage, and the contents are guided into the vortex chamber R to form a vortex, and then ejected from the ejection hole 7p. The number of grooves in the converging passage is preferably 2 to 10, more preferably 2 to 8.

[0170] Figure 15 The operating part 6a of the ejection member 6 has an internal passage (first pipe 61) that is approximately L-shaped and a fitting part 63 for inserting the nozzle 7. The fitting part 63 is a generally cylindrical recess. A cylindrical protrusion (cylindrical part 64) is provided on the inner bottom surface of the fitting part 63.

[0171] The cylindrical portion 64 is the part embedded within the foot 71 of the nozzle 7 when the nozzle 7 is installed on the operating part 6a. In the state where the nozzle 7 is installed (i.e.... Figure 15 In this state, the side circumferential surface of the cylindrical portion 64 is slightly separated from the inner circumferential surface of the foot portion 71. The gap and internal passage (first conduit 61) formed by this separation of the cylindrical portion 64 and the foot portion 71 constitute the internal passage 74 of the ejection member, through which the contents collected from the aerosol container pass during ejection. Furthermore, as... Figure 15 As shown, the front end face of the cylindrical part 64 abuts against the inner bottom surface of the nozzle 7.

[0172] The nozzle 7 is a bottomed cylindrical shape, consisting of a base plate 72 and cylindrical feet 71 erected around one surface of the base plate 72. The base plate 72 is a disc-shaped portion with a specified thickness, forming a recess 73 and a groove connecting to the recess 73. An ejection hole 7p for communication with the outside is formed at the center of the inner bottom surface of the recess 73.

[0173] By mounting the nozzle 7 to the operating part 6a, the opening surface of the recess 73 is closed by abutting against the front end face of the cylindrical part 64. Thus, a vortex chamber R is formed in the ejection member 6, defined by the recess 73 and the front end face of the cylindrical part 64. The size of the vortex chamber R is not particularly limited. As an example, the vortex chamber R is a cylindrical space with a diameter of 0.8 to 2.0 mm, preferably 1.0 to 1.5 mm, and a height (depth) of approximately 0.05 to 0.2 mm. Furthermore, the shape of the vortex chamber R is not limited to a cylindrical shape. The vortex chamber R can be any shape with an inner circumference that allows the introduced contents to swirl.

[0174] Similarly, the opening of the slot is closed by mounting the nozzle 7 to the operating part 6a, thereby abutting against the front end face of the cylindrical part 64. As a result, a converging passage connected to the vortex chamber R is formed in the ejection member 6.

[0175] The vortex chamber R is a roughly cylindrical space with grooves connected around it. The grooves are passages connecting the internal passage of the ejection component to the vortex chamber R, forming a side opening at one end connected to the internal passage of the ejection component and a side opening at the other end connected to the vortex chamber R.

[0176] The slots are arranged radially at approximately equal intervals relative to the swirl chamber R. Each slot is formed to guide the contents along the inner periphery of the swirl chamber R. By forming the slots in this direction, the contents introduced into the swirl chamber R through the slots do not directly face the ejection port 7p, but instead swirl within the swirl chamber R along its inner periphery. After swirling within the swirl chamber R, the contents are ejected from the ejection port 7p located at the center of the swirl chamber R.

[0177] The size of the ejection orifice 7p is not particularly limited. As an example, the diameter of the ejection orifice 7p is preferably about 0.1 to 0.8 mm, more preferably about 0.2 to 0.6 mm. With an ejection orifice 7p of this size, since the contents are ejected in a wide-range diffusion manner after sufficient swirling in the swirl chamber R, the ejected particle size itself becomes smaller, making it easier to generate many ultrafine bubbles. Therefore, the particle size D90, where the volumetric accumulation distribution of ultrafine bubbles in the liquid composition is 90%, tends to be smaller. Furthermore, ultrafine bubbles are easily dispersed at a high concentration.

[0178] Figure 16 This is a schematic diagram illustrating one embodiment of the ejection member 8 used for manufacturing an aerosol product of a liquid composition according to one embodiment of the present invention.

[0179] like Figure 16 As shown, the ejector component 8 does not have branch components and is equipped with a nozzle 9 that is linearly connected to the ejector hole 91 from the first conduit 81. In this ejector component 8, the nozzle 9 is connected to the first conduit 81 via the valve 3 (see reference 91). Figure 14 The contents that have been collected and passed through the first conduit 81 are ejected from the ejector hole 91 at a high jet pressure, which can powerfully impart the liquid composition containing ultrafine bubbles to the object.

[0180] The nozzle 9 protrudes outward and is generally cylindrical. The inner diameter of the passage within the nozzle 9, from the root 92 to the ejection hole 91, is approximately the same. The ejection hole 91 may be the same as or smaller than the inner diameter. The inner diameter of the ejection hole 91 is preferably, for example, 0.2 to 3.0 mm, more preferably 0.3 to 2.5 mm. Therefore, the contents ejected by the ejection member 8 flow linearly in the passage within the nozzle 9 and are ejected to the outside from the ejection hole 91.

[0181] Furthermore, when it is necessary to apply passage resistance to the contents flowing within the nozzle to suppress the vaporization of dissolved compressed gas, and to generate ultrafine bubbles at a high concentration when ejected to the outside, the size of the passage within the nozzle 9, for example, the inner diameter, is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm. Additionally, the length of the passage within the nozzle 9 is preferably 3 to 20 mm, more preferably 5 to 15 mm.

[0182] The aerosol product 1 in this embodiment can be adopted. Figure 14 The ejector component 8a shown is used instead of the ejector component 8. Figure 14 This is a schematic diagram of the ejection component 8a used to manufacture the aerosol products of the liquid compositions of Examples 11 and 12 described below. Figure 14The ejector component shown has a generally cylindrical nozzle 81a. The diameter of the passage within the nozzle 81a is approximately the same as the diameter of the injection hole 82a. Like ejector component 8, ejector component 8a does not have branching components. Ejector component 8a originates from the first conduit 81 (see reference 82a). Figure 16 The connection is linear from valve 3 to injection port 82a. As a result, from valve 3 (see reference...) Figure 14 The contents collected and passed through the first conduit 81 are ejected from the injection hole 82a with high jet force, becoming a jet containing ultrafine bubbles, which can powerfully apply to the object.

[0183] Returning to the overall description of aerosol product 1, in this embodiment, the liquid L containing dissolved compressed gas in aerosol product 1 is appropriately slowed down during its passage through the spray passage after being taken out from valve 3, and is sprayed out from the spray hole 52 in the form of ultrafine bubbles generated along with the vaporization of the dissolved compressed gas, thus constituting a liquid composition.

[0184] The above description pertains to one embodiment of the present invention. Specifically, in the above embodiment, a method and a liquid composition are illustrated by filling an aerosol product with a liquid as a stock solution, dissolving compressed gas in the liquid and spraying it out, thereby generating and dispersing ultrafine bubbles of compressed gas in the liquid.

[0185] Furthermore, the liquid composition can be used to fill a dispensing container into a dispensing product, where the liquid composition is manufactured in a pressurized, sealed tank. Examples of such dispensing containers include... Figure 14 From the viewpoint of being able to stably disperse ultrafine bubbles, containers that can be filled with liquid compositions in a liquid-tight state are preferred, including a double-layered aerosol container with an inner bag housed in the container body, an aerosol container without an inner bag housed in the container body, a pump container with a direct pressure / accumulator pump housed in the container body, a pump container with an inner bag housed in the container body and having a double-layered structure without an air pump, and small packages.

[0186] [Third Implementation] The aerosol product of one embodiment (third embodiment) of the present invention is an aerosol product for spraying a liquid composition (also referred to as a jet). The liquid composition is a liquid composition in which ultrafine bubbles are dispersed. The particle size D90 of the ultrafine bubbles, with a volumetric cumulative distribution value of 90%, is 50-300 nm. The number of ultrafine bubbles is 4.0 × 10⁻⁶ per milliliter. 7One or more. It consists of an aerosol container filled with the original liquid and the propellant, and a spray button installed on the aerosol container and having a spray hole formed therein. When the propellant is sprayed from the spray hole, the spray force at a distance of 5 cm from the spray hole is 10 to 400 mN. These will be described separately below. Furthermore, in the following description, for structures identical to those described in the first or second embodiment, the disclosure in the first or second embodiment will be referenced and appropriately omitted.

[0187] (original solution) There are no particular restrictions on the stock solution filled in the aerosol container. The stock solution is the same as the liquid described in the first or second embodiment.

[0188] The solvent content in the stock solution is preferably 60% by mass or more, more preferably 70% by mass or more. Furthermore, the solvent content in the stock solution is preferably 100% by mass or less, more preferably 99.9% by mass or less. By keeping the solvent content within the above range, the stock solution readily dissolves the amount of propellant required to generate ultrafine bubbles at a high concentration. In particular, when the stock solution contains 60% by mass or more water, the ultrafine bubbles in the aerosol product propellant have small particle sizes and narrow particle size distribution widths, resulting in uniform ultrafine particle size and a stable effect that is easily sustained. Furthermore, the components exemplified in aqueous or oil-based solvents can also be added to the solvent as additives or active ingredients.

[0189] The stock solution may contain various active ingredients, surfactants, thickeners, powders, and any other components. Examples of these are the same as those described in the first or second embodiment.

[0190] When an active ingredient is included in the formulation, its content is not particularly limited. As an example, the content of the active ingredient in the stock solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the content of the active ingredient in the stock solution is preferably 20% by mass or less, more preferably 15% by mass or less. By keeping the content of the active ingredient within the above ranges, it is easy to obtain the effects based on the formulated active ingredient.

[0191] Surfactants are appropriately formulated to improve cleaning effectiveness and enhance the retention of ultrafine bubbles by allowing them to adsorb dirt components.

[0192] There are no particular restrictions on surfactants. In particular, by using ionic surfactants, aerosol products can easily achieve effects such as reducing the adhesion of positively or negatively charged pollen and other dispersed substances.

[0193] When a surfactant is included in the formulation, the amount of surfactant is not particularly limited. As an example, the surfactant content in the stock solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the surfactant content in the stock solution is preferably 10% by mass or less, more preferably 8% by mass or less. By keeping the surfactant content within the above ranges, the aerosol product can easily achieve the effect based on the surfactant content.

[0194] Thickeners are appropriately proportioned to increase the viscosity of the original solution or impart thixotropy, thereby slowing down the generation rate of ultrafine particles in the spray, adjusting the particle size of ultrafine particles, and making ultrafine bubbles disperse more stably.

[0195] There is no particular limitation on the content of the thickener. As an example, the content of the thickener in the stock solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. Furthermore, the content of the thickener in the stock solution is preferably 5% by mass or less, more preferably 3% by mass or less. By keeping the content of the thickener within the above range, the aerosol product can easily achieve the effect of adjusting the particle size of the ultrafine bubbles dispersed in the spray, resulting in a more stable dispersion of the ultrafine bubbles.

[0196] When powder is included in the formulation, the powder content is not particularly limited. As an example, the powder content in the concentrate is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. Furthermore, the powder content in the concentrate is preferably 5% by mass or less, more preferably 3% by mass or less. By keeping the powder content within the above range, the aerosol product can easily achieve the effect based on the proportioned powder.

[0197] There are no particular limitations on the manufacturing method of the stock solution. For example, the stock solution can be prepared by adding the active ingredients to a solvent to dissolve or disperse them.

[0198] (Injector) There are no particular limitations on the propellant. To give an example, the propellant is a compressed gas that remains a gas even when filled into an aerosol container, or a liquefied gas that partially liquefies and separates into liquid and gas when filled into an aerosol container.

[0199] (Compressed gas) There are no particular limitations on the compressed gas. As an example, it is preferable to have a compressed gas with a solubility of 0.001 mL or more relative to 1 mL of the stock solution (solvent) at 25°C and atmospheric pressure, more preferably 0.005 mL or more. Furthermore, the solubility of the compressed gas is preferably 5 mL or less, more preferably 3 mL or less. By ensuring that the solubility of the compressed gas in the stock solution is within the above-mentioned range, the compressed gas filled into the aerosol container can be dissolved in the stock solution at a suitable concentration. As a result, ultrafine bubbles are easily generated at high concentrations in the jet, with a small particle size distribution and easily uniform particle size.

[0200] More specifically, the compressed gases are nitrogen (0.0141 mL relative to 1 mL of water and 0.137 mL relative to 1 mL of ethanol), hydrogen (0.0175 mL relative to 1 mL of water and 0.0784 mL relative to 1 mL of ethanol), helium (0.0087 mL relative to 1 mL of water and 0.0294 mL relative to 1 mL of ethanol), sulfur hexafluoride (0.00545 mL relative to 1 mL of water), air (0.0167 mL relative to 1 mL of water), oxygen (0.0283 mL relative to 1 mL of water and 0.222 mL relative to 1 mL of ethanol), carbon dioxide (0.759 mL relative to 1 mL of water and 2.706 mL relative to 1 mL of ethanol), nitrous oxide (0.0588 mL relative to 1 mL of water), argon (0.0306 mL relative to 1 mL of water and 0.239 mL relative to 1 mL of ethanol), and mixtures thereof. When using compressed gases with low solubility (less than 1.0 mL relative to 1 mL of solvent), the content of smaller ultrafine bubbles in the aerosol product tends to increase, which is therefore preferable.

[0201] Compressed gas is filled into an aerosol container containing a stock solution, and is saturated with the stock solution. The amount of compressed gas saturated with the stock solution is preferably 30 ppm or more, more preferably 40 ppm or more, per 1 mL of stock solution at 25°C. Furthermore, the amount of compressed gas saturated with the stock solution at 25°C is preferably 80,000 ppm or less, more preferably 70,000 ppm or less. By keeping the amount of compressed gas saturated within the above range, when sprayed into the atmosphere with a specific jetting force, a large number of ultrafine bubbles are easily generated in the spray. In this embodiment, the amount of compressed gas saturated with the stock solution is a value calculated based on the volume of the stock solution filled into the pressure-resistant container, the volume of the gas phase portion of the compressed gas, the filling amount of the compressed gas, and the pressure at which the compressed gas dissolves in the stock solution within the pressure-resistant container at 25°C and reaches equilibrium.

[0202] (Liquefied gas) There are no particular restrictions on liquefied gases. As an example, liquefied gases include: lipophilic liquefied gases, such as liquefied petroleum gas composed of propane, n-butane, isobutane and mixtures thereof; hydrofluoroolefins with boiling points below 5°C, such as trans-1,3,3,3-tetrafluoroprop-1-ene and mixtures thereof; or amphiphilic liquefied gases composed of dimethyl ether and mixtures thereof, etc.

[0203] The liquefied gas preferably contains liquefied petroleum gas composed of propane, n-butane, isobutane, and mixtures thereof, as well as hydrofluoroolefins with boiling points below 5°C, such as trans-1,3,3,3-tetrafluoroprop-1-ene, and mixtures thereof, i.e., lipophilic liquefied gases. Therefore, when the spray is used on the human body, the ultrafine bubbles easily adhere to the skin surface, easily achieving a long-term effect of removing sebum and other dirt from the application area. Furthermore, by immersing the item to be cleaned in the spray, it easily achieves a cleaning effect such as adsorption and removal of oil stains. Further, when using a solvent containing water, the lipophilic liquefied gas easily separates from the original liquid within the aerosol container. However, the lipophilic liquefied gas is always saturated and dissolved in the original liquid. Therefore, the spray produces a large number of ultrafine bubbles that are also easily stabilized.

[0204] Liquefied gas is filled into pressure-resistant container 2. A portion of the liquefied gas dissolves in the original liquid, but it also exists in the gas phase. When the amount of liquefied gas added exceeds the saturation dissolution amount in the original liquid, the liquefied gas separates from the original liquid, forming a liquid phase. At the moment of filling pressure-resistant container 2, the amount of liquefied gas dissolved relative to 1 mL of original liquid, converted to liquid, is preferably 0.0001 mL or more, more preferably 0.0003 mL or more. Furthermore, the amount of liquefied gas dissolved is preferably 0.5 mL or less, more preferably 0.3 mL or less. By keeping the amount of liquefied gas dissolved within the above range, the sprayed material easily generates a large number of ultrafine bubbles after ejection. In this embodiment, the amount of liquefied gas dissolved refers to the amount of liquefied gas dissolved in the original liquid at 25°C.

[0205] More specifically, the liquefied gas is liquefied petroleum gas of propane (0.014 mL relative to 1 m water), butane (0.010 mL relative to 1 m water) and mixtures thereof, trans-1,3,3,3-tetrafluoroprop-1-ene (0.000319 mL relative to 1 m water), dimethyl ether (0.106 mL relative to 1 m water) and mixtures thereof, etc.

[0206] <Manufacturing Method of Aerosol Products> Aerosol products can be manufactured by filling a pressure-resistant container with a concentrate, installing and sealing a valve in the container, filling the propellant through the valve, saturating the propellant with the concentrate, and installing a dispensing button on the valve. Alternatively, the propellant can be filled before installing the valve into the pressure-resistant container.

[0207] Figure 1 This is a schematic cross-sectional view of the aerosol product 1 of this embodiment. Figure 1 The image shows aerosol product 1 in its non-use state. For example... Figure 1 As shown, the aerosol product 1 of this embodiment mainly includes: a pressure-resistant container 2 filled with contents consisting of a stock liquid L and a propellant; a valve 3 installed in the pressure-resistant container 2; and a spray button 4 installed in the valve 3, forming a spray hole 52 for spraying the contents. The various structures will be described below. However, the structure of the aerosol product 1 is not limited to this embodiment. Therefore, the structure of the aerosol product 1 shown below is an example, and appropriate design changes can be made. Furthermore, the liquid phase La is the phase formed when the liquefied gas (e.g., liquefied petroleum gas) is separated from the liquid L. Therefore, the liquid phase La can be omitted when the propellant is a compressed gas (e.g., nitrogen).

[0208] (Pressure vessel) The pressure container 2 is a container used to fill the stock solution L under pressure and in a sealed state. The pressure container 2 can be of a general shape. In this embodiment, the pressure container 2 is a bottomed cylindrical shape with an opening at the top. The opening is a filling port for filling the stock solution L. The pressure container 2 is fitted with the following valve 3 at the opening for sealing.

[0209] •Pressure-resistant container 2 The pressure container 2 becomes an aerosol container by installing and closing the valve 3 described below at its opening. The material of the pressure container 2 is not particularly limited. Examples of such materials include metals such as aluminum and tin-plated iron; synthetic resins such as polyethylene terephthalate and polyester; and pressure-resistant glass. Furthermore, the pressure container 2 can have an inner bag inside. The inner bag is a bag-shaped container that can be compressed by the pressure of the propellant. The inner bag is filled with the aforementioned stock solution L in a liquid-tight state. The material of the inner bag is not particularly limited. As an example, the material of the inner bag can be polyolefins such as polyethylene, ethylene-vinyl alcohol copolymers, polyamides, and other synthetic resins. Additionally, the inner bag can be a single layer of the aforementioned synthetic resin or a laminate of multiple layers.

[0210] (Valve 3) Valve 3 is a component installed at the opening of pressure vessel 2 and used to seal the interior of pressure vessel 2. It includes: a valve mechanism 31, which can switch the connection / cut-off between the interior and exterior of pressure vessel 2 by moving up and down; and a housing 32, which forms a defined internal space for accommodating valve mechanism 31. Valve mechanism 31 includes: a valve stem 33, having a valve stem hole 33a that communicates with the exterior by pressing downward; a valve stem rubber 34 that seals the valve stem hole 33a; and a spring 35 that always applies force to valve stem 33 vertically upward from below. A liquid phase inlet hole 32a is formed at the lower part of housing 32, which communicates the interior space of housing 32 with the interior of pressure vessel 2 via pipe 36. If valve stem hole 33a is opened by the action of valve 3, the liquid L filled in pressure vessel 2 is drawn into housing 32 from the opening at the lower end of pipe 36 through liquid phase inlet hole 32a by the pressure of the injector, passes through the passage in valve stem hole 33a and valve stem 33, and is sent to injection button 4.

[0211] There are no particular limitations on the method of filling the pressure container 2 with the stock solution L and the propellant. As an example, the stock solution L is filled through the opening of the pressure container 2, the valve 3 is fixed at the opening of the pressure container 2, and then the propellant is filled through the valve stem to saturate and dissolve the propellant in the stock solution. Alternatively, the propellant can be filled from below between the pressure container 2 and the valve, and then the valve can be fixed to the opening of the pressure container.

[0212] When the propellant is a compressed gas, the pressure inside the aerosol container after the propellant is filled and saturated dissolved in the stock solution L is preferably 0.3 to 1.0 MPa (gauge pressure) at 25°C, specifically 0.4 to 0.9 MPa (gauge pressure). By adjusting the pressure inside the aerosol container to the above range, even if the pressure inside the aerosol container decreases due to the reduction of the stock solution in the aerosol container caused by the propellant injection, the compressed gas remains in the stock solution within the above-mentioned dissolved amount range, enabling the generation of ultrafine bubbles at a high concentration.

[0213] (Jet button 4) The spray button 4 is a component used to open valve 3 by operation, spraying out the stock solution L containing the propellant collected through valve 3. The spray button 4 mainly consists of the user-operated control unit 5. Figure 1 As shown, the injection button 4 is installed on the valve stem 33 of the valve 3.

[0214] • Operations Section 5 The operating part 5 is a generally cylindrical portion, having one end with a mounting hole 51 for mounting the valve stem 33 and the other end with a spray hole 52 for spraying contents. The mounting hole 51 is a cylindrical connection port formed at one end of the operating part 5, into which the valve stem 33 is inserted. An internal passage for contents removed from the valve 3 to pass through is opened at the bottom of the mounting hole 51. The other end of the internal passage opens as the spray hole 52.

[0215] The internal passage is a series of passages (jet passages) through which the contents received from valve 3 pass to the jet hole 52. A generally L-shaped first conduit 53 is formed within the internal passage for the contents received from valve 3 to pass through. A generally cylindrical branch member 54, which causes the contents passing through the first conduit 53 to collide and change the flow direction to branch the flow path, and a nozzle 55 covering the circumferential surface of the branch member 54 are installed within the space of the first conduit 53. Additionally, 2 to 6 grooves (not shown) are formed at the downstream end of the first conduit 53, diffusing outwards from the first conduit 53. Therefore, by inserting the branch member 54 into the cylindrical space, a diffusion passage is formed between the grooves and the branch member 54, allowing the contents to flow outwards. The width of the diffusion passage is preferably 0.2 to 0.6 mm.

[0216] The nozzle 55 is a bottomed cylindrical shape, consisting of a generally disc-shaped bottom and a peripheral portion covering the circumferential surface of the branch member 54. Two to ten, preferably two to eight, grooves (not shown) are formed at the bottom of the nozzle 55, which allow contents passing between the outer peripheral surface of the branch member 54 and the inner peripheral surface of the peripheral portion to flow from the outer periphery toward the centrally formed injection hole 52. Furthermore, a vortex chamber R for swirling the contents is formed at the central portion where these grooves converge. By mounting the nozzle 55 on the branch member 54, a converging passage is formed between the grooves and the branch member 54, allowing the contents to flow into the vortex chamber R. By keeping the number of grooves within the aforementioned range, the propellant to be sprayed experiences strong resistance as it flows through the converging passage, suppressing the vaporization of the dissolved propellant. Therefore, the propellant readily vaporizes after being sprayed from the injection hole. As a result, the propellant readily generates ultrafine bubbles at a high concentration immediately after spraying.

[0217] A jet hole 52 is provided at the center of the vortex chamber. Furthermore, multiple transverse grooves (not shown) are formed on the outer peripheral surface of the branch member 54 to allow the contents flowing from the diffusion path on the first conduit 53 side to the converging path at the bottom of the nozzle 55 into the outer peripheral branch. The transverse grooves can be spiral-shaped to lengthen the flow path and increase the flow resistance to further slow the flow rate. The width of the converging path is preferably 0.1 to 0.5 mm. The size of the vortex chamber R is not particularly limited. As an example, the vortex chamber R is a cylindrical space with a diameter of 0.3 to 2.0 mm, preferably 0.4 to 1.5 mm, and a height (depth) of approximately 0.05 to 0.2 mm. Furthermore, the shape of the vortex chamber R is not limited to a cylindrical shape. The vortex chamber R can be any inner peripheral shape in which the introduced contents can swirl.

[0218] The contents, drawn in from valve 3 and passing through the first conduit 53, collide with the branch member 54, causing the flow direction to change radially via the diffusion path. Next, the contents pass through the transverse groove between the outer circumferential surface of the branch member 54 and the inner circumferential surface of the nozzle 55, causing the flow direction to change centrally via the converging path. The contents are then guided into the vortex chamber, where they become a vortex and are ejected from the injection port 52.

[0219] There is no particular limitation on the inner diameter of the first conduit 53. The inner diameter of the first conduit 53 is appropriately adjusted according to the desired injection speed, etc. As an example, the inner diameter of the first conduit 53 is 0.5 to 3 mm.

[0220] Furthermore, the orifice diameter of the injection orifice 52 is not particularly limited. The orifice diameter of the injection orifice 52 can be appropriately adjusted according to the desired injection speed, etc. As an example, the orifice diameter of the injection orifice 52 is preferably 0.2 mm or more, more preferably 0.25 mm or more. Additionally, the orifice diameter of the injection orifice 52 is preferably 1.0 mm or less, more preferably 0.8 mm or less. By keeping the diameter of the injection orifice within the above range, the flow rate of the propellant is throttled by the injection orifice, and it encounters appropriate flow resistance when passing through the converging passage, thereby suppressing the vaporization of the propellant. Therefore, the propellant easily vaporizes after being injected from the injection orifice to the outside. As a result, the propellant readily generates ultrafine bubbles at a high concentration immediately after injection.

[0221] There are no particular restrictions on the cross-sectional shape of the injection hole 52. As an example, the cross-sectional shape of the injection hole 52 can be circular, elliptical, rectangular, etc.

[0222] In the setting Figure 1In the injection button 4 of the diffusion and convergence channels shown, the contents, which are forced out by the pressure inside the aerosol container and collected from the valve 3, are subject to channel resistance as they pass through the first pipe 53, diffusion channel, transverse groove, and convergence channel. The injection force when injected from the injection hole should be adjusted to 10 mN or more at a distance of 5 cm from the injection hole, preferably 15 mN or more. Furthermore, the injection force should be adjusted to 400 mN or less, preferably 100 mN or less, and more preferably 90 mN or less. By adjusting the injection force to such a level, the vaporization rate of the propellant dissolved in the contents flowing through the injection button's channels is suppressed, making it easier to vaporize when injected from the injection hole to the outside, and increasing the number of ultrafine bubbles. Additionally, regarding... Figure 1 Regarding the spray button, when the contents are sprayed out from the spray nozzle, the particles of the sprayed material themselves become smaller, resulting in smaller and more numerous microbubbles. As a result, the sprayed material from aerosol product 1, under atmospheric pressure, is sprayed with a specific spray force due to the resistance within the spray button 4, thus easily generating microbubbles at a high concentration in the sprayed material, and the particle size distribution width of the microbubbles becomes smaller. Therefore, in the resulting sprayed material, the microbubbles are stably dispersed, easily achieving the effect of microbubbles.

[0223] Figure 2 This is a schematic diagram illustrating one embodiment of the spray button 6 used in the aerosol product of this embodiment.

[0224] Figure 2 The injection button 6 shown has an operating part 6a integrally formed with a branch member 62, and a nozzle 7 is mounted thereon. Regarding the injection button 6 with such a converging passage, from the valve 3 (see reference...) Figure 1 The contents of the first conduit 61 pass through the gap between the outer peripheral surface of the branch member 62 and the inner peripheral surface of the nozzle 7. The converging passage changes the flow direction to a central direction, and the contents are guided into the vortex chamber R to form a vortex, which is then ejected from the injection hole 7p. The number of grooves in the converging passage is preferably 2 to 10, more preferably 2 to 8. The width of the converging passage is preferably 0.1 to 0.5 mm.

[0225] Figure 2 The operating part 6a of the injection button 6 has an approximately L-shaped internal passage (first pipe 61) and a fitting part 63 for inserting the nozzle 7. The fitting part 63 is a generally cylindrical recess. A cylindrical protrusion (cylindrical part 64) is provided on the inner bottom surface of the fitting part 63.

[0226] The cylindrical portion 64 is the part embedded within the foot 71 of the nozzle 7 when the nozzle 7 is installed onto the operating part 6a. In the state where the nozzle 7 is installed (i.e.... Figure 2In this state, the side circumferential surface of the cylindrical portion 64 is slightly separated from the inner circumferential surface of the foot portion 71. The gap formed by this separation of the cylindrical portion 64 and the foot portion 71, and the first conduit 61, are part of the spray passage 74 through which the contents collected from the aerosol container pass during spraying. Additionally, as... Figure 2 As shown, the front end face of the cylindrical part 64 abuts against the inner bottom surface of the nozzle 7.

[0227] The nozzle 7 is a bottomed cylindrical shape, consisting of a base plate 72 and cylindrical feet 71 erected around one surface of the base plate 72. The base plate 72 is a disc-shaped portion with a specified thickness, forming a recess 73 and a groove connecting to the recess 73. A spray hole 7p for communication with the outside is formed at the center of the inner bottom surface of the recess 73.

[0228] By mounting the nozzle 7 to the operating part 6a, the opening surface of the recess 73 is closed by abutting against the front end surface of the cylindrical part 64. Thus, the injection button 6 forms a swirl chamber R defined by the recess 73 and the front end surface of the cylindrical part 64. The size of the swirl chamber R is not particularly limited. As an example, the swirl chamber R is a cylindrical space with a diameter of 0.3 to 2.0 mm, preferably 0.4 to 1.5 mm, and a height (depth) of approximately 0.05 to 0.2 mm. Furthermore, the shape of the swirl chamber R is not limited to a cylindrical shape. The swirl chamber R can be any shape with an inner circumference that allows the introduced contents to swirl.

[0229] Similarly, the opening of the slot is closed by mounting the nozzle 7 to the operating part 6a, thereby abutting against the front end face of the cylindrical part 64. Thus, the injection button 6 forms a converging passage connected to the swirl chamber R.

[0230] The vortex chamber R is a generally cylindrical space with grooves connected around its perimeter. These grooves are passageways connecting the cylindrical portion 64 and the foot portion 71 to the vortex chamber R. The grooves are arranged radially at approximately equal intervals relative to the vortex chamber R. Here, each groove is formed to guide the contents along the inner periphery of the vortex chamber R. By forming the grooves in this direction, the contents guided into the vortex chamber R through the grooves do not directly face the injection hole 7p, but instead swirl within the vortex chamber R along its inner periphery. After swirling within the vortex chamber R, the contents are ejected from the injection hole 7p located at the center of the vortex chamber R.

[0231] The size of the injection orifice 7p is not particularly limited. As an example, the diameter of the injection orifice 7p is preferably about 0.1 to 0.8 mm, more preferably about 0.2 to 0.6 mm. With an injection orifice 7p of this size, the contents, forced out by the pressure inside the aerosol container and collected from the valve 3, encounter passage resistance as they pass through the first pipe 53, the gap, and the converging passage. The injection force when ejected from the injection orifice can be adjusted to 10 mN or more at a distance of 5 cm from the injection orifice, preferably 15 mN or more. Furthermore, the injection force can be adjusted to 400 mN or less, preferably 150 mN or less, more preferably 100 mN or less. By adjusting the injection force to this level, the vaporization rate of the propellant dissolved in the contents flowing through the injection button passage is suppressed, making it easier to vaporize when ejected from the injection orifice to the outside, and increasing the number of ultrafine bubbles. Furthermore, regarding... Figure 2 As for the spray button, when the contents are sprayed out from the spray hole, the particles of the sprayed material themselves become smaller, and the particle size of the generated ultrafine bubbles becomes smaller and the number of bubbles increases.

[0232] Figure 3 This is a schematic diagram illustrating one embodiment of the spray button 8 used in the aerosol product of this embodiment. (See diagram for reference.) Figure 3 As shown, the injection button 8 has no branch components and is equipped with a nozzle 9 that is linearly connected to the injection hole 91 from the first pipeline 81. In this injection button 8, the nozzle 9 is connected to the first pipeline 81 in a straight line. (Refer to...) Figure 1 The contents that have been collected and passed through the first conduit 81 are ejected from the jet hole 91 with high jet force, which can powerfully impart the jet containing ultrafine bubbles to the target object.

[0233] The nozzle 9 protrudes outward and is generally cylindrical. The inner diameter of the passage within the nozzle 9, from the root 92 to the spray hole 91, is approximately the same. The spray hole 91 may be the same as or smaller than the inner diameter. The inner diameter of the spray hole 91 is preferably, for example, 0.2 to 3.0 mm, more preferably 0.3 to 2.5 mm. Therefore, the contents sprayed using the spray button 8 flow linearly in the passage within the nozzle 9 and are sprayed outward from the spray hole 91.

[0234] Furthermore, when it is necessary to apply passage resistance to the contents flowing within the nozzle to suppress the vaporization of the dissolved propellant, and to generate ultrafine bubbles at a high concentration when sprayed to the outside, the size of the passage within the nozzle 9, for example, the inner diameter, is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm. Additionally, the length of the passage within the nozzle 9 is preferably 3 to 20 mm, more preferably 5 to 15 mm.

[0235] With a nozzle of this size, the contents, forced out by the pressure within the aerosol container and collected from valve 3, encounter resistance as they pass through the nozzle's passage and spray orifice 91. The spray force at a distance of 5 cm from the spray orifice should be adjusted to 10 mN or more, preferably 30 mN or more, and more preferably 80 mN or more. Furthermore, the spray force should be adjusted to 400 mN or less, preferably 350 mN or less. By adjusting the spray force to this level, the dissolved propellant in the contents flowing through the spray button's passage vaporizes and is sprayed out through the spray orifice, effectively delivering the propellant to the target object while containing numerous ultrafine bubbles.

[0236] The aerosol product 1 in this embodiment can be adopted. Figure 43 The spray button 8a shown is used instead of spray button 8. Figure 43 This is a schematic diagram of the spray button 8a used to manufacture the aerosol products of the sprays in Examples C10 and C11 described below. Figure 43 The spray button 8a shown has a generally cylindrical nozzle 81a. The diameter of the passage inside the nozzle 81a is approximately the same as the diameter of the spray orifice 82a. Like spray button 8, spray button 8a does not have branching components. The spray component 8a originates from the first conduit 81 (see reference 82a). Figure 3 The connection is linear from valve 3 to injection port 82a. As a result, from valve 3 (see reference...) Figure 1 The contents collected and passed through the first conduit 81 are ejected from the injection hole 82a with high jet force, becoming a jet containing ultrafine bubbles, which can powerfully apply to the object.

[0237] The inner diameter of the injection hole 82a is preferably 0.2 to 3.0 mm, more preferably 0.3 to 2.5 mm. The length of the passage inside the nozzle 81a is preferably 3 to 20 mm, more preferably 5 to 15 mm.

[0238] With a nozzle 81a of this size, the contents, forced out by the pressure within the aerosol container and collected from the valve 3, encounter resistance as they pass through the passage within the nozzle 81a and the spray hole 82a. Therefore, the spray force when sprayed from the spray hole 82a is adjusted to 10 mN or more, preferably 30 mN or more, at a distance of 5 cm from the spray hole. Furthermore, the spray force is adjusted to 400 mN or less, preferably 300 mN or less. By adjusting the spray force to such a level, the dissolved propellant in the contents flowing through the spray button's passage vaporizes and is sprayed out from the spray hole, powerfully delivering the propellant to the target object while containing numerous ultrafine bubbles.

[0239] Returning to the overall description of aerosol product 1, in this embodiment, the stock solution L containing the propellant is appropriately slowed down during its passage through the spraying path after being taken out from the valve 3, and is sprayed from the spraying hole 52 in the form of ultrafine bubbles generated by the vaporization of the dissolved propellant, which can impart the effect of ultrafine bubbles to the target object.

[0240] Furthermore, when using compressed gas as the propellant, when the pressure inside the aerosol container is 0.8 MPa at 25°C, the spray rate of the propellant ejected from the spray hole is preferably 0.6 g / s or more, more preferably 0.7 g / s or more. Additionally, the spray rate is preferably 6.0 g / s or less, more preferably 5.5 g / s or less. Specifically, when the spray button has a converging path, the spray rate is preferably 2.0 g / s or less. By adjusting the spray rate to such a level, the flow rate of the propellant of aerosol product 1 through the spray hole is adjusted, making it easy to adjust the spray force at a distance of 5 cm from the spray hole to 10–400 mN, and easily generating ultrafine bubbles at a high concentration.

[0241] (Ultra-fine bubbles) Ultrafine bubbles are tiny bubbles dispersed in the spray from the contents of the aerosol product of the present invention.

[0242] The particle size D90, where the volumetric cumulative distribution value of the ultrafine bubbles is 90%, is preferably 50 nm or more, and more preferably 70 nm or more. Furthermore, the particle size D90, where the volumetric cumulative distribution value of the ultrafine bubbles is 90%, is preferably 300 nm or less, and more preferably 250 nm or less. By ensuring that D90 is within the above range, the sprayed material contains a majority of tiny bubbles with an average particle size in the nanometer range (1–1000 nm), particularly ultrafine bubbles of 10–300 nm. As a result, the ultrafine bubbles in the obtained sprayed material can be dispersed at a high concentration and stably for a long period. In addition, since the ultrafine bubbles have increased opportunities to contact the target object, it is easier to obtain the following effects: the effect of easily obtaining effective components adsorbed on the ultrafine bubbles; the effect of ultrafine bubbles adsorbing onto the target object to inhibit the adhesion of dirt components; and the effect of ultrafine bubbles adsorbing dirt components for purification.

[0243] Furthermore, in this embodiment, the method for measuring the particle size D90 with a cumulative distribution value of 90% can, for example, use a nano-tracking particle size measuring device (NanoSight NS300, manufactured by Malvern Panalytical Ltd) to measure the recovered jet after the jet is adjusted to 25°C.

[0244] According to the aforementioned nano-tracking particle size measuring device, in addition to D90, it can also measure particle size D50 with a cumulative distribution value of 50% and particle size D10 with a cumulative distribution value of 10%. Furthermore, the nano-tracking particle size measuring device can also measure the number of ultrafine bubbles per milliliter.

[0245] The D50 of the ultrafine bubbles is preferably 30 nm or more, more preferably 50 nm or more. Furthermore, the D50 of the ultrafine bubbles is preferably 200 nm or less, more preferably 170 nm or less. Furthermore, the D10 of the ultrafine bubbles is preferably 10 nm or more, more preferably 20 nm or more. Furthermore, the D10 of the ultrafine bubbles is preferably 150 nm or less, more preferably 100 nm or less. By keeping the D50 and D10 within the above ranges, the sprayed material contains a majority of tiny bubbles with an average particle size of nanometers (1–1000 nm), particularly ultrafine bubbles of 10–300 nm. As a result, the obtained sprayed material can contain ultrafine bubbles at a high concentration and stably dispersed over a long period.

[0246] In the ultrafine bubbles of this embodiment, the proportion of bubbles with a particle size exceeding 300 nm is preferably 10% or less, and more preferably 5% or less, in the total number of bubbles.

[0247] The number of ultrafine bubbles immediately after generation (e.g., 15 minutes after generation) is preferably 4.0 × 10⁻⁶ per milliliter. 7 More than one, preferably 4.5 × 10 7 More than one, preferably 8.0 × 10 7 More than one. By keeping the number of ultrafine bubbles within the above range, the jet can contain ultrafine bubbles at a high concentration.

[0248] The bubbles constituting the ultrafine bubbles are preferably bubbles formed by the vaporization of compressed gas dissolved in the original liquid under pressure through decompression. Therefore, the ultrafine bubbles in the jet have small particle sizes, the ultrafine particles are easily uniform in size, they are easily dispersed at high concentrations, and the effects based on ultrafine bubbles can be easily obtained over a long period.

[0249] The present invention has been described above with respect to one embodiment. The present invention is not particularly limited to the above embodiment. Furthermore, the above embodiment mainly describes an embodiment of the invention having the following structure.

[0250] (1) A liquid composition dispersed with ultrafine bubbles, wherein the volumetric cumulative distribution value of the ultrafine bubbles is 90% and the particle size D90 is 50-300 nm, and the number of ultrafine bubbles is 4.0 × 10⁻⁶ per milliliter. 7 More than one.

[0251] Based on this structure, the ultrafine bubbles in the liquid composition have a particle size as small as 50–300 nm with a volumetric cumulative distribution of 90%, and a density of 4.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion. These ultrafine bubbles exhibit excellent dispersion stability. As a result, for example, liquid compositions can easily achieve effects based on ultrafine bubbles over a long period of time.

[0252] (2) According to the liquid composition described in (1), the ultrafine bubbles are bubbles formed by the vaporization of liquefied gas at atmospheric pressure and 25°C, and the number of ultrafine bubbles is 5.0 × 10⁻⁶ per milliliter. 7 More than one.

[0253] Due to this structure, the dispersion stability of ultrafine bubbles is excellent. As a result, for example, liquid compositions can easily achieve the effect of ultrafine bubbles based on liquefied gas over a long period of time.

[0254] (3) According to the liquid composition described in (2), the liquefied gas contains an oleophilic liquefied gas, which is a liquefied petroleum gas composed of propane, n-butane, isobutane and mixtures thereof, hydrofluoroolefins with a boiling point of less than 5°C and mixtures thereof.

[0255] Based on this structure, when the liquid composition is used on the human body, the ultrafine bubbles easily adhere to the skin surface, achieving a long-lasting effect of removing sebum and other dirt from the application area. Furthermore, by immersing the liquid composition, it easily achieves a cleaning effect that absorbs and removes oil and other contaminants.

[0256] (4) The liquid composition according to any one of (1) to (3) contains water.

[0257] Based on this structure, the liquid composition can easily disperse ultrafine bubbles with a stable particle size for a long time without dissolving, and the effect can be sustained.

[0258] (5) According to the liquid composition described in (2), the liquefied gas contains dimethyl ether.

[0259] Based on this structure, liquid compositions can more easily obtain ultrafine bubbles with particle sizes within a certain range.

[0260] (6) The liquid composition according to any one of (1) to (5) contains a monohydric alcohol having 2 to 3 carbon atoms.

[0261] Based on this structure, liquid compositions can more easily obtain ultrafine bubbles with particle sizes within a certain range.

[0262] (7) A sprayed product made by filling a spray container with any one of the liquid compositions described in (1) to (6).

[0263] Based on this structure, the spray product can be used by spraying out a liquid composition with a high concentration of dispersed ultrafine bubbles.

[0264] (8) According to the liquid composition described in (1), the ultrafine bubbles are bubbles of compressed gas.

[0265] With this structure, the chances of ultrafine bubbles in the liquid composition coming into contact with the target object are increased, making it easier to obtain effects based on ultrafine bubbles over a long period of time.

[0266] (9) According to the liquid composition described in (8), the amount of the compressed gas that dissolves relative to 1 mL of liquid at 25°C and atmospheric pressure is 0.001 to 5 mL.

[0267] Due to this structure, the particle size of the ultrafine bubbles becomes smaller, making it easier to disperse them at high concentrations.

[0268] (10) The liquid composition according to (1), (8) or (9) contains more than 60% by mass of water in the liquid.

[0269] Based on this structure, the ultrafine bubbles in the liquid composition have small particle sizes and narrow particle size distribution widths, and the ultrafine particles are of uniform size, making it easy to maintain a stable effect.

[0270] (11) The liquid composition according to any one of (1), (8) to (10), wherein the liquid composition contains a monohydric alcohol having 2 to 3 carbon atoms.

[0271] Based on this structure, the particle size of ultrafine bubbles in the liquid composition can be easily reduced.

[0272] (12) A sprayed product made by filling a spray container with any one of the liquid compositions described in (1), (8) to (11).

[0273] Based on this structure, the spray product can be used by spraying out a liquid composition with a high concentration of dispersed ultrafine bubbles, thereby easily achieving the desired effect on the target object.

[0274] (13) An aerosol product for spraying a liquid composition, said liquid composition being a liquid composition dispersed with ultrafine bubbles, said ultrafine bubbles having a volumetric cumulative distribution value of 90% and a particle size D90 of 50–300 nm, said ultrafine bubbles having a number of 4.0 × 10⁻⁶ per milliliter. 7The aerosol product comprises an aerosol container filled with a stock solution and a propellant, and a spray button installed in the aerosol container and having a spray hole formed thereon. When the propellant is sprayed from the spray hole, the spray force at a distance of 5 cm from the spray hole is 10 to 400 mN.

[0275] Based on this structure, the spray material ejected from the aerosol product under atmospheric pressure is propelled with a specific spray force by the resistance within the spray button, thus easily generating ultrafine bubbles at a high concentration in the spray material, and the particle size distribution width of the ultrafine bubbles becomes smaller. Therefore, the resulting spray material has ultrafine bubbles that are stably dispersed, easily achieving the effect of ultrafine bubbles.

[0276] (14) According to the aerosol product described in (13), the propellant is a compressed gas.

[0277] Based on this structure, the compressed gas dissolved in the original liquid within the aerosol container is easily vaporized in the spray material by being ejected to the outside. As a result, the particle size of the ultrafine bubbles, with a cumulative volume distribution of 90% in the spray material, easily decreases to 50–300 nm, and readily increases at a rate of 4.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion.

[0278] (15) According to the aerosol product described in (14), the amount of the compressed gas dissolved at 25°C and atmospheric pressure relative to 1 mL of the original solution is 0.001 to 5 mL.

[0279] With this structure, compressed gas dissolved in the original liquid within the aerosol container is easily vaporized in the spray material when ejected to the outside. As a result, ultrafine bubbles are easily generated at high concentrations in the spray material, and the particle size distribution width of these ultrafine bubbles tends to be smaller.

[0280] (16) According to the aerosol product described in (13), the propellant is a liquefied gas.

[0281] Based on this structure, the liquefied gas dissolved in the original liquid within the aerosol container is easily vaporized in the spray material by being ejected to the outside. As a result, the particle size of the ultrafine bubbles, with a cumulative volume distribution of 90% in the spray material, easily decreases to 50–300 nm, and readily disperses at a rate of 5.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion.

[0282] (17) According to any one of (13) to (16) the aerosol product, the spray button has a converging passage, in which grooves are formed to converge the sprayed material toward the spray hole, the number of grooves being 2 to 10.

[0283] Due to this structure, the propellant to be sprayed experiences strong flow resistance in the converging channel, suppressing the vaporization of the propellant dissolved in the original liquid. Therefore, the propellant readily vaporizes after being sprayed from the nozzle. As a result, the propellant readily generates ultrafine bubbles at a high concentration immediately after spraying.

[0284] (18) The diameter of the spray hole is 0.2 to 1.0 mm for the aerosol product described in any one of (13) to (17).

[0285] With this structure, the flow rate of the propellant is throttled by the injection orifice, and it encounters appropriate flow resistance as it passes through the converging path, thus suppressing propellant vaporization. Therefore, the propellant readily vaporizes after being ejected from the injection orifice. As a result, the propellant readily generates ultrafine bubbles at a high concentration immediately after injection.

[0286] Furthermore, the first embodiment described above specifically illustrates an embodiment of the invention having the following structure.

[0287] (1) A liquid composition dispersed with ultrafine bubbles, wherein the ultrafine bubbles are formed by the vaporization of liquefied gas at atmospheric pressure and 25°C, the ultrafine bubbles having a volumetric cumulative distribution value of 90% and a particle size D90 of 50–300 nm, and the number of ultrafine bubbles being 5.0 × 10⁻⁶ per milliliter. 7 More than one.

[0288] Based on this structure, the ultrafine bubbles in the liquid composition have a particle size as small as 50–300 nm, with 90% of the bubbles being cumulatively distributed by volume, and a density of 5.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion. These ultrafine bubbles exhibit excellent dispersion stability. As a result, for example, liquid compositions can easily achieve the effect of ultrafine bubbles based on liquefied gas over a long period of time.

[0289] (2) According to the liquid composition described in (1), the liquefied gas contains an oleophilic liquefied gas, which is a liquefied petroleum gas composed of propane, n-butane, isobutane and mixtures thereof, hydrofluoroolefins with a boiling point below 5°C and mixtures thereof.

[0290] Based on this structure, when the liquid composition is used on the human body, the ultrafine bubbles easily adhere to the skin surface, achieving a long-lasting effect of removing sebum and other dirt from the application area. Furthermore, by immersing the liquid composition, it easily achieves a cleaning effect that absorbs and removes oil and other contaminants.

[0291] (3) The liquid composition according to (1) or (2) contains water.

[0292] Based on this structure, the liquid composition can easily disperse ultrafine bubbles with a stable particle size for a long time without dissolving, and the effect can be sustained.

[0293] (4) According to the liquid composition described in (1), the liquefied gas contains dimethyl ether.

[0294] Based on this structure, liquid compositions can more easily obtain ultrafine bubbles with particle sizes within a certain range.

[0295] (5) The liquid composition according to (1) or (2) contains a monohydric alcohol having 2 to 3 carbon atoms.

[0296] Based on this structure, liquid compositions can more easily obtain ultrafine bubbles with particle sizes within a certain range.

[0297] (6) A sprayed product made by filling a spray container with any one of the liquid compositions of (1) to (5).

[0298] Based on this structure, the spray product can be used by spraying out a liquid composition with a high concentration of dispersed ultrafine bubbles.

[0299] Furthermore, the second embodiment described above specifically illustrates an embodiment of the invention having the following structure.

[0300] (1) A liquid composition having ultrafine bubbles dispersed in a liquid, wherein the ultrafine bubbles are compressed gas bubbles, the ultrafine bubbles having a particle size D90 of 50–300 nm for a 90% volumetric cumulative distribution value, and the number of ultrafine bubbles being 4.0 × 10⁻⁶ per milliliter. 7 More than one.

[0301] Based on this structure, the ultrafine bubbles in the liquid composition have a particle size as small as 50–300 nm, with 90% of the bubbles being cumulatively distributed by volume, and a density of 4.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion. These ultrafine bubbles exhibit excellent dispersion stability. As a result, for example, in liquid compositions, the ultrafine bubbles have increased opportunities to come into contact with the target material, making it easier to obtain ultrafine bubble-based effects over a long period.

[0302] (2) According to the liquid composition described in (1), the amount of the compressed gas that dissolves relative to 1 mL of liquid at 25°C and atmospheric pressure is 0.001 to 5 mL.

[0303] Due to this structure, the particle size of the ultrafine bubbles becomes smaller, making it easier to disperse them at high concentrations.

[0304] (3) The liquid composition according to (1) or (2) contains more than 60% by mass of water in the liquid.

[0305] Based on this structure, the ultrafine bubbles in the liquid composition have small particle sizes and narrow particle size distribution widths, and the ultrafine particles are of uniform size, making it easy to maintain a stable effect.

[0306] (4) The liquid composition according to any one of (1) to (3) contains a monohydric alcohol having 2 to 3 carbon atoms.

[0307] Based on this structure, the particle size of ultrafine bubbles in the liquid composition can be easily reduced.

[0308] (5) A sprayed product made by filling a spray container with any one of the liquid compositions described in (1) to (4).

[0309] Furthermore, the third embodiment described above specifically describes an embodiment of the invention having the following structure.

[0310] (1) An aerosol product comprising an aerosol container filled with a stock solution and a propellant and a spray button installed in the aerosol container and having a spray hole, wherein when the propellant is sprayed from the spray hole, the spray force at a distance of 5 cm from the spray hole is 10 to 400 mN.

[0311] Based on this structure, the sprayed material from the aerosol product, under atmospheric pressure, is propelled with a specific spraying force by the resistance within the spray button's flow path. Therefore, it is easy to generate ultrafine bubbles at a high concentration in the sprayed material, and the particle size distribution width of the ultrafine bubbles is reduced. Consequently, the ultrafine bubbles are stably dispersed in the sprayed material, easily achieving the effect of ultrafine bubbles.

[0312] (2) According to the aerosol product described in (1), the propellant is a compressed gas.

[0313] Based on this structure, compressed gas dissolved in the original liquid within the aerosol container is easily vaporized in the ejected material when sprayed to the outside. As a result, in the ejected material, the particle size of ultrafine bubbles, representing 90% of the volumetric cumulative distribution, easily decreases to 50–300 nm, and readily increases at a rate of 4.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion.

[0314] (3) According to the aerosol product described in (2), the amount of the compressed gas that dissolves relative to 1 mL of the original liquid at 25°C and atmospheric pressure is 0.001 to 5 mL.

[0315] Based on this structure, compressed gas dissolved in the original liquid within the aerosol container is easily vaporized in the ejected material when sprayed to the outside. As a result, ultrafine bubbles are easily generated at high concentrations in the ejected material, and the particle size distribution width of these ultrafine bubbles tends to be smaller.

[0316] (4) According to the aerosol product described in (1), the propellant is a liquefied gas.

[0317] Based on this structure, liquefied gases dissolved in the original liquid within the aerosol container are easily vaporized in the ejected material when sprayed to the outside. As a result, in the ejected material, the particle size of ultrafine bubbles, representing 90% of the volumetric cumulative distribution, easily decreases to 50–300 nm, readily achieving a vaporization rate of 5.0 × 10⁻⁶ per milliliter. 7 More than one high-concentration dispersion.

[0318] (5) The aerosol product described in any one of (1) to (4) has a converging passage in which grooves are formed to converge the sprayed material toward the spray hole, and the number of grooves is 2 to 10.

[0319] Due to this structure, the propellant to be sprayed experiences strong flow resistance in the converging channel, suppressing the vaporization of the propellant dissolved in the original liquid. Therefore, the propellant readily vaporizes after being sprayed from the nozzle. As a result, the propellant readily generates ultrafine bubbles at a high concentration immediately after spraying.

[0320] (6) The diameter of the spray hole is 0.2 to 1.0 mm for the aerosol product described in any one of (1) to (5).

[0321] With this structure, the flow rate of the propellant is throttled by the injection orifice, and it encounters appropriate flow resistance as it passes through the converging path, thereby suppressing the vaporization of the propellant. Therefore, the propellant readily vaporizes after being injected from the orifice. As a result, the propellant readily generates ultrafine bubbles at a high concentration immediately after injection.

[0322] Example The present invention will now be described in more detail through examples. However, the present invention is not limited to these examples.

[0323] <Examples related to the first embodiment> (Example A1) Fill the pressure vessel with 90g (90% by mass) of water as a liquid, and then fix the valve to the opening to seal it. Further, fill the valve stem with 10g (10% by mass) of liquefied petroleum gas, and install it on the valve stem. Figure 1 An aerosol product was prepared using an ejector component (with 4 slots in the diffusion path, 4 slots in the converging path, and an ejection orifice of Φ0.3). A liquid composition was prepared by ejecting 20 mL of the resulting aerosol product into another cup-shaped container using the ejector component.

[0324] (Example A2) Installation of the aerosol product in Example A1 Figure 3 The ejection component shown (jet hole Φ1.2) was used to produce an aerosol product.

[0325] (Example A3) Except for using hydrofluoroolefin (HFO-1234ze: trans-1,3,3,3-tetrafluoroprop-1-ene) instead of liquefied petroleum gas, the aerosol product is manufactured using the same method as in Example A1. Figure 1 The ejection component ejects the contents into other containers, creating a liquid composition.

[0326] (Example A4) Use of the aerosol product of Example A3 Figure 3 The ejection component sprays the contents into other containers, creating a liquid composition.

[0327] (Example A5) Except for using dimethyl ether instead of liquefied petroleum gas, the aerosol product is manufactured using the same method as in Example A1, using... Figure 1 The ejection component ejects the contents into other containers, creating a liquid composition.

[0328] (Example A6) Use of the aerosol product of Example A5 Figure 3 The ejection component sprays the contents into other containers, creating a liquid composition.

[0329] (Comparative Example A1) The water used in Example A1 is used.

[0330] (Example A7) Fill the pressure vessel with 90g (90% by mass) of ethanol as a liquid, and then secure the valve to the opening to seal it. Further, fill the valve stem with 10g (10% by mass) of liquefied petroleum gas, and install it on the valve stem. Figure 3 The ejector component shown (jet orifice Φ1.2) was used to produce an aerosol product. Using the ejector component, 20 mL of the resulting aerosol product was ejected into another cup-shaped container to create a liquid composition.

[0331] (Comparative Example A2) Ethanol, which was used in Example A7, was used.

[0332] For the liquid compositions obtained in Examples A1-A7 and Comparative Examples A1-A2, the D90, D50, D10, and number of particles were measured using a nano-tracking particle size analyzer (NanoSight NS300, manufactured by Malvern Panalytical Ltd). The liquid compositions were set to 25°C and measured after 15 minutes and 1 day. The results are shown in Table 1. Additionally, a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition is presented in... Figures 4 to 13 As shown. Figure 4 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A1 15 minutes after spraying. Figure 5 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A1 one day after spraying. Figure 6 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A3 after 15 minutes of spraying. Figure 7 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A3 one day after spraying. Figure 8 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A5 after 15 minutes of spraying. Figure 9 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A5 one day after spraying. Figure 10 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Comparative Example A1. Figure 11 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A7 after 15 minutes of spraying. Figure 12 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Example A7 one day after spraying. Figure 13 This is a graph showing the relationship between the particle size and concentration of ultrafine bubbles dispersed in the liquid composition of Comparative Example A2.

[0333] Table 1

[0334] As shown in Table 1 and Figures 4-5 As shown, in Example A1, where water was used as the liquid and liquefied petroleum gas was dispersed as ultrafine bubbles, the liquid composition after 15 minutes of spraying exhibited ultrafine bubbles concentrated in a particularly small range of values ​​within the nanometer scale (1–1000 nm), with a D90 of 165.8 nm and a concentration of 6.14 × 10⁻⁶ ppm per mL. 8 One microbubble was sprayed, and 1 mL of the liquid composition after one day contained 6.99 × 10⁻⁶ microbubbles.8 Each ultrafine bubble. The same applies to the liquid composition of Example A2.

[0335] As shown in Table 1 and Figures 6-7 As shown, in Example A3, where water was used as the liquid and hydrofluoroolefins were dispersed as ultrafine bubbles, the liquid composition after 15 minutes of spraying exhibited ultrafine bubbles concentrated in a particularly small range of values ​​at the nanoscale (1–1000 nm), with a D90 of 159.5 nm and 4.02 × 10⁻⁶ particles per mL. 8 One ultrafine bubble; after one day of spraying, 1 mL of the liquid composition contained 3.66 × 10⁻⁶ microbubbles. 8 Each ultrafine bubble. The same applies to the liquid composition of Example A4.

[0336] As shown in Table 1 and Figures 8-9 As shown, in Example A5, where water was used as the liquid and dimethyl ether was dispersed as the ultrafine bubbles, the liquid composition after 15 minutes of spraying exhibited ultrafine bubbles concentrated in a particularly small range at the nanoscale (1–1000 nm), with a D90 of 197.1 nm and 1.04 × 10⁻⁶ particles per mL. 8 One ultrafine bubble; after one day of spraying, 1 mL of the liquid composition contained 8.11 × 10⁻⁶ microbubbles. 7 Each ultrafine bubble. The same applies to the liquid composition of Example A6.

[0337] On the other hand, as shown in Table 1 and Figure 10 As shown, in the liquid composition of Comparative Example A1, which uses only water, although the bubbles are nanoscale (1–1000 nm), the D90 is 378.5 nm, and 6.25 × 10⁻⁶ per mL. 6 A few.

[0338] Additionally, as shown in Table 1 and Figures 11-12 As shown, in Example A7, where ethanol is used as the liquid and liquefied petroleum gas is dispersed in ultrafine bubbles, the ultrafine bubbles are concentrated in a particularly small range even at the nanometer scale (1–1000 nm), with a D90 of 221.9 nm and 1.07 × 10⁻⁶ particles per mL. 8 One microbubble; after one day of spraying, 1 mL of the liquid composition contained 4.22 × 10⁻⁶ microbubbles. 8 Each ultra-fine bubble.

[0339] On the other hand, as shown in Table 1 and Figure 13 As shown, in the liquid composition of Comparative Example A2, which uses only ethanol, the bubbles are concentrated in a particularly small range even at the nanoscale (1–1000 nm), with a D90 of 21.5 nm, but only 5.03 × 10⁻⁶ in 1 mL. 4 A few.

[0340] <Examples related to the second implementation> (Example B1) Water is filled into an outer container (without an inner bag) as the liquid. A valve is then installed on the outer container, through which nitrogen gas is filled. The container is stored at room temperature for 3 days to allow a portion of the nitrogen to dissolve into the water to create an aerosol product. The pressure inside the container is 0.8 MPa (25°C). Based on the full fill volume of the outer container, the amount of water filled, the amount of nitrogen filled, and the pressure, the nitrogen dissolution rate relative to 1 mL of water is calculated to be 130 ppm. The valve stem orifice is Φ0.4, the lower orifice of the shell is Φ1.0, there are no transverse holes, and a suction tube is installed at the bottom of the shell, allowing liquid to be sprayed out from the bottom of the outer container. The valve is equipped with… Figure 14 The image shows an ejection component (ejection orifice: Φ0.3) with diffusion channels (number of channels: 4) and convergence channels (number of channels: 4). 20 mL of the resulting aerosol product was ejected from the aerosol product into another cup-shaped container, generating and dispersing ultrafine bubbles to create a liquid composition.

[0341] (Example B2) Installation of aerosol products in Example 1 Figure 15 The ejector component (ejector hole: Φ0.33, number of channels for converging passages: 3) ejects the liquid composition into other containers. Furthermore, the pressure inside the containers is 0.8 MPa (25°C).

[0342] (Example B3) Installation of aerosol products in Example B1 Figure 15 The ejector component (ejector hole: Φ0.3, number of channels for converging passages: 8) ejects the liquid composition into other containers. Furthermore, the pressure inside the containers is 0.8 MPa (25°C).

[0343] (Example B4) Installation of aerosol products in Example B1 Figure 16 The ejector component (ejector hole: Φ1.2, passage length: 10.5mm) was used to eject the liquid composition into other containers. Furthermore, the pressure inside the containers was 0.8MPa (25°C).

[0344] (Example B5) Towards Figure 14The pressure vessel shown has an inner bag (a single layer of polyethylene) filled with water as a liquid. Nitrogen gas is then filled into the space between the outer container and the inner bag, and a valve is installed. The inner bag is liquid-tightly filled with water. The valve stem orifice is Φ0.4, and the transverse holes in the shell are configured to open in the water (liquid phase) but not in the gas phase. After being stored at room temperature for 3 days, some of the nitrogen gas permeates through the inner bag and dissolves saturated in the water, thus producing an aerosol product. Figure 14 The ejection component shown (number of diffusion channels: 4, number of converging channels: 4, ejection orifice: Φ0.3). Furthermore, the pressure inside the container is 0.8 MPa (25°C), and the nitrogen solubility relative to 1 mL of water, calculated based on the outer container's fill volume, water volume, nitrogen volume, and pressure, is 130 ppm. 20 mL of the resulting aerosol product was ejected from another container, generating and dispersing ultrafine bubbles to create a liquid composition.

[0345] (Example B6) Except that carbon dioxide gas is used instead of nitrogen gas, the aerosol product is manufactured using the same method as in Example B1, using... Figure 14 The contents were ejected from the ejector component (ejector hole: Φ0.3) to create a liquid composition. Furthermore, the pressure inside the container was 0.8 MPa (25°C), and the solubility of carbon dioxide gas relative to 1 mL of water was calculated to be 13,700 ppm based on the full volume of the outer container, the amount of water filled, the amount of carbon dioxide gas filled, and the pressure.

[0346] (Example B7) use Figure 16 The ejection component (ejection orifice: Φ1.2, passage length: 10.5 mm) ejected the aerosol product of Example B6 into other containers to prepare a liquid composition. Furthermore, the pressure inside the containers was 0.8 MPa (25°C).

[0347] (Comparative Example B1) The water used in Example B1 was used.

[0348] (Comparative Example B2) The water used in Example B1 was filled into a bottle, and a direct-pressure pump was installed on the bottle. The bottle was then stored at room temperature for 3 days to manufacture the pump product. Figure 14 The ejector component shown (ejector hole: Φ0.3). A direct-pressure pump of the resulting pump product was used to eject 20 mL of water into other containers, creating a liquid composition.

[0349] (Comparative Example B3) In Example B1, an aerosol product was fitted with a button (dispensing orifice Φ0.3, manufactured by Mitani Valves Co., Ltd.) with a flow adjustment mechanism as described in Patent Document 1, and the product was sprayed into another container to create a liquid composition. Furthermore, the pressure inside the container was 0.8 MPa (25°C).

[0350] (Example B8) Except for using ethanol instead of water and carbon dioxide gas instead of nitrogen gas, an aerosol product was manufactured using the same method as in Example B1, and installed... Figure 16 A liquid composition was prepared by ejecting the contents through an ejection component (ejection hole: Φ1.2, passage length: 10.5 mm). Furthermore, the pressure inside the container was 0.8 MPa (25°C), and the solubility of carbon dioxide gas relative to 1 mL of ethanol was calculated to be 54,000 ppm based on the full fill volume of the outer container, the amount of ethanol filled, the amount of carbon dioxide gas filled, and the pressure.

[0351] (Comparative Example B4) Ethanol, which was used in Example B8, was used.

[0352] (Comparative Example B5) The ethanol used in Example B8 was filled into a bottle, and a direct-pressure pump was installed on the bottle. The bottle was then stored at room temperature for 3 days to manufacture the pump product. Figure 14 The ejector component shown (ejector orifice: Φ0.3). A direct-pressure pump of the resulting pump product was used to eject 20 mL of ethanol into other containers, thus creating a liquid composition.

[0353] For the liquid compositions obtained in Examples B1-B8 and Comparative Examples B1-B5, the D90, D50, D10, and particle number of the liquid compositions adjusted to 25°C were measured using a nano-tracking particle size analyzer (NanoSight NS300, manufactured by Malvern Panalytical Ltd). Furthermore, the measurements were performed without diluting the liquid compositions with solvents. The results are shown in Table 2. Additionally, graphs showing the relationship between particle size and concentration are provided for Examples B1, B6, B8, and Comparative Examples B1-B5. Figures 17-26 As shown.

[0354] Table 2

[0355] As shown in Table 2 and Figures 17-18 As shown, in the liquid composition of Example B1, which uses water as the liquid and nitrogen gas, the ultrafine bubbles are concentrated in a particularly small range of values ​​at the nanoscale (1-1000 nm), with a D90 of 187.4 nm and 3.19 × 10⁻⁶ particles per mL. 8One ultrafine bubble was sprayed, and the liquid composition after one day contained 1.33 × 10⁻⁶ microbubbles per mL. 8 Each contains an ultrafine bubble. The same applies to the liquid compositions in Examples B2 to B5.

[0356] As shown in Table 2 and Figures 19-20 As shown, in the liquid composition of Example B6, where water is used as the liquid and carbon dioxide gas is dispersed as ultrafine bubbles, the ultrafine bubbles are concentrated in a particularly small range of values ​​at the nanometer scale (1-1000 nm), with a D90 of 213.4 nm and 1.67 × 10⁻⁶ particles per mL. 8 One microbubble was observed, and after one day of spraying, 1 mL of the liquid composition contained 3.32 × 10⁻⁶ microbubbles. 7 Each ultrafine bubble. The same applies to the liquid composition of Example B7.

[0357] On the other hand, as shown in Table 2 and Figure 21 As shown, in the liquid composition of Comparative Example B1 using only water, although the bubbles were nanoscale (1–1000 nm), many bubbles with a diameter exceeding 300 nm (e.g., 400 nm) were also found, with a D90 of 378.5 nm and 6.25 × 10⁻⁶ per mL. 6 A few.

[0358] On the other hand, as shown in Table 2 and Figure 22 As shown, in the liquid composition of Comparative Example B2, where water is used as the liquid and a direct-pressure pump is employed, the bubbles are concentrated in a particularly small range of values ​​at the nanoscale (1–1000 nm), with a D90 of 82.7 nm, but only 2.02 × 10⁻⁶ in 1 mL. 7 A few.

[0359] On the other hand, as shown in Table 2 and Figure 23 As shown, in Comparative Example B3, where water was used as the liquid and a button with a flow adjustment mechanism was used, the concentration of water in 1 mL was 2.49 × 10⁻⁶. 8 There were a relatively large number of bubbles, but many with a diameter exceeding 300 nm (e.g., 800 nm) were also found, with a D90 of 680.6 nm.

[0360] Additionally, as shown in Table 2 and Figure 24 As shown, in Example B8, where ethanol is used as the liquid and carbon dioxide gas is dispersed in ultrafine bubbles, the ultrafine bubbles are concentrated in a particularly small range of values ​​at the nanoscale (1-1000 nm), with a D90 of 181.4 nm and 4.81 × 10⁻⁶ ppm per mL. 7 Each ultra-fine bubble.

[0361] On the other hand, as shown in Table 2 and Figure 25As shown, in the liquid composition of Comparative Example B4, which uses only ethanol, the bubbles are also concentrated in a particularly small range of values ​​at the nanoscale (1–1000 nm), with a D90 of 21.5 nm, but only 5.03 × 10⁻⁶ in 1 mL. 4 Very few.

[0362] On the other hand, as shown in Table 2 and Figure 26 As shown, in Comparative Example B5, where ethanol was used as the liquid and a direct-pressure pump was employed, although the ultrafine bubbles were nanoscale (1–1000 nm) and the D90 was 238.2 nm, the density per 1 mL was 2.87 × 10⁻⁶. 7 A few.

[0363] (Example B9) Water was filled into an outer container (without an inner bag) as the liquid. A valve was then installed on the outer container, through which nitrogen gas was filled. The container was stored at room temperature for 3 days to allow some of the nitrogen to dissolve into the water, thus creating an aerosol product. The pressure inside the container was 0.8 MPa (25°C). Based on the full fill volume of the outer container, the amount of water filled, the amount of nitrogen filled, and the pressure, the nitrogen dissolution rate relative to 1 mL of water was calculated to be 130 ppm. The valve stem orifice was Φ0.4, the lower orifice of the housing was Φ1.0, and there were no horizontal holes. A suction tube was installed at the bottom of the housing, allowing liquid to be sprayed out from the bottom of the outer container. Figure 14 The image shows an ejection component (ejection orifice: Φ0.36) with diffusion channels (number of channels: 4) and convergence channels (number of channels: 4). 20 mL of the resulting aerosol product was ejected from the aerosol product into another cup-shaped container, generating and dispersing ultrafine bubbles to create a liquid composition.

[0364] (Example B10) Installation of aerosol products in Example B9 Figure 15 The ejector component (ejector hole: Φ0.60, number of channels for converging passages: 4) ejects the liquid composition into other containers. Furthermore, the pressure inside the containers is 0.8 MPa (25°C).

[0365] (Example B11) Installation of aerosol products in Example B9 Figure 27 The ejector component 8a (ejector hole 82a: Φ0.35, passage length: 6mm) was used to eject the liquid composition into other containers. Furthermore, the pressure inside the containers was 0.8MPa (25°C).

[0366] (Example B12) Installation of aerosol products in Example B9 Figure 27The ejector component 8a (ejector hole 82a: Φ1.2, passage length: 6mm) was used to eject the liquid composition into other containers. Furthermore, the pressure inside the containers was 0.8MPa (25°C).

[0367] (Example B13) Installation of aerosol products in Example B9 Figure 16 The ejector component (ejector hole: Φ0.3, passage length: 10.5 mm) was used to eject the liquid composition into other containers. Furthermore, the pressure inside the containers was 0.8 MPa (25°C).

[0368] (Example B14) Water was filled into an outer container (without an inner bag) as the liquid. A valve was then installed on the outer container, through which nitrogen gas was filled. The container was stored at room temperature for 3 days to allow some of the nitrogen to dissolve into the water, thus creating an aerosol product. Furthermore, the pressure inside the container was 0.8 MPa (25°C). Based on the full fill volume of the outer container, the amount of water filled, the amount of nitrogen filled, and the pressure, the nitrogen solubility relative to 1 mL of water was calculated to be 130 ppm. The valve stem orifice was Φ0.3, and the lower orifice of the housing was also Φ0.3, with no transverse orifice. A suction tube was installed at the bottom of the housing, allowing liquid to be sprayed out from the bottom of the outer container. Figure 14 The image shows an ejection component (ejection orifice: Φ0.36) with diffusion channels (number of channels: 4) and convergence channels (number of channels: 4). 20 mL of the resulting aerosol product was ejected from the aerosol product into another cup-shaped container, generating and dispersing ultrafine bubbles to create a liquid composition.

[0369] For the liquid compositions obtained in Examples B9 to B14, the D90, D50, D10, and number of particles of the liquid compositions adjusted to 25°C were measured using a nano-tracking particle size analyzer (NanoSight NS300, manufactured by Malvern Panalytical Ltd). Furthermore, the measurements were performed without diluting the liquid compositions with solvents. The results are shown in Table 3. Additionally, for Examples B10, B11, and B14, graphs showing the relationship between particle size and concentration are presented in... Figures 28-30 As shown.

[0370] Table 3

[0371] <Examples related to the third implementation> (Example C1) Towards Figure 1The pressure vessel shown is filled with water as the stock solution. A valve is then installed on the pressure vessel, through which nitrogen gas is filled. It is stored at room temperature for 3 days to allow some of the nitrogen to dissolve into the water to saturate. Furthermore, the pressure inside the vessel is 0.8 MPa (25°C). Based on the pressure vessel's full fill volume, the amount of water filled, the amount of nitrogen filled, and the pressure, the calculated nitrogen dissolution rate per 1 mL of water is 130 ppm. The valve stem orifice is Φ0.4, the lower orifice of the shell is Φ1.0, there are no transverse orifices, and a suction pipe is installed at the bottom of the shell, allowing the stock solution to be sprayed out from the bottom of the pressure vessel. [The last sentence appears to be incomplete and possibly refers to a valve installation.] Figure 1 The spray button (spray orifice: Φ0.3) shown has diffusion channels (number of channels: 4) and converging channels (number of channels: 4) to produce an aerosol product. 20 mL of the resulting aerosol product was sprayed from the aerosol product into another cup-shaped container, generating and dispersing ultrafine bubbles to create a spray. The spray rate at 25°C was 0.8 g / s.

[0372] (Example C2) Installation of aerosol products in Example C1 Figure 2 The spray button (spray hole: Φ0.33, number of channels for converging: 3) was activated and sprayed into other containers, creating a jet. Furthermore, the pressure inside the container was 0.8 MPa (25°C), and the spray rate was 1.6 g / s.

[0373] (Example C3) Installation of aerosol products in Example C1 Figure 2 The spray button (spray hole: Φ0.3, number of channels for converging: 8) was activated and sprayed into other containers, creating a jet. Furthermore, the pressure inside the container was 0.8 MPa (25°C), and the spray rate was 0.7 g / s.

[0374] (Example C4) Installation of aerosol products in Example C1 Figure 3 The spray button (spray hole: Φ1.2, passage length: 10.5mm) was pressed and sprayed into other containers to create a spray. Furthermore, the pressure inside the container was 0.8MPa (25℃), and the spray rate was 5.4g / s.

[0375] (Example C5) Except that carbon dioxide gas was used instead of nitrogen gas, an aerosol product was manufactured using the same method as in Example C1, and installed... Figure 1 The spray button was pressed and the gas was sprayed into other containers, creating a spray. In addition, the pressure inside the container was 0.8 MPa (25°C). Based on the full filling volume of the pressure-resistant container, the amount of water filled, the amount of carbon dioxide gas filled, and the pressure, the solubility of carbon dioxide gas relative to 1 mL of water was calculated to be 13,700 ppm, and the spray rate was 0.7 g / s.

[0376] (Example C6) Installation of aerosol products in Example C5 Figure 3 The spray button (spray hole: Φ1.2, passage length: 10.5mm) was pressed and sprayed into other containers to create a spray. Furthermore, the pressure inside the container was 0.8MPa (25℃), and the spray rate was 4.2g / s.

[0377] (Comparative Example C1) The water used in Example C1 was used.

[0378] (Comparative Example C2) The water used in Example C1 was filled into a bottle, and a direct-pressure pump was installed on the bottle. The bottle was then stored at room temperature for 3 days to manufacture the pump product. [The pump was then installed...] Figure 1 The spray button is shown (spray orifice: Φ0.3). The direct-pressure pump of the obtained pump product is used to spray 20 mL of water into other containers, creating a spray.

[0379] (Comparative Example C3) In Example C1, the aerosol product was fitted with a button (spray hole: Φ0.3, manufactured by Mitani Valves Co., Ltd.) with a flow adjustment mechanism as described in Patent Document 1, and sprayed into another container to create a jet. Furthermore, the pressure inside the container was 0.8 MPa (25°C), and the spray rate was 0.5 g / s.

[0380] (Example C7) Towards Figure 1 The pressure vessel shown is filled with ethanol as the stock solution. A valve is then installed on the pressure vessel, through which carbon dioxide gas is introduced. It is stored at room temperature for 3 days to allow some of the carbon dioxide gas to dissolve into the ethanol. Furthermore, the pressure inside the vessel is 0.8 MPa (25°C). Based on the full fill volume of the pressure vessel, the amount of ethanol and carbon dioxide gas introduced, and the pressure, the calculated solubility of carbon dioxide gas relative to 1 mL of ethanol is 54,000 ppm. The valve stem orifice is Φ0.4, the lower orifice of the body is Φ1.0, there are no transverse holes, and a suction tube is installed at the bottom of the body, allowing the stock solution to be sprayed out from the bottom of the pressure vessel. Valve usage... Figure 3 The spray button (spray hole: Φ1.2) was pressed and sprayed into other containers, creating a spray. The spray rate at 25°C was 4.5 g / s.

[0381] (Comparative Example C4) Ethanol, which was used in Example C8, was used.

[0382] (Comparative Example C5) The ethanol used in Example C8 was filled into a bottle, and a direct-pressure pump was installed on the bottle. The bottle was then stored at room temperature for 3 days to manufacture the pump product. Figure 1 The injection button is shown (injection orifice: Φ0.3). Operating the direct-pressure pump of the resulting pump product and injecting 20 mL of ethanol into another container creates a spray.

[0383] (Measurement of jet force) The aerosol products and pump products obtained in Examples C1 to C7 and Comparative Examples C2, C3, and C5 were immersed in a constant temperature water bath at 25°C for 30 minutes. The products were then adjusted to 25°C, and the jetting force at a position 5 cm away from the jet hole was measured using a digital force gauge FGP-0.5 (manufactured by Nidec Shinpo Co., Ltd., Japan). The results are shown in Table 4.

[0384] (Measurement of particle size and number) The aerosol products, pump products, or concentrates obtained in Examples C1-C7 and Comparative Examples C1-C5 were adjusted to 25°C, and D90, D50, D10, and the number of particles were measured using a nano-tracking particle size analyzer (NanoSight NS300, manufactured by Malvern Panalytical Ltd). Furthermore, the measurements were performed without diluting the sprayed material with solvent. The results are shown in Table 4. Additionally, a graph showing the relationship between particle size and concentration is presented in... Figures 31-42 As shown.

[0385] Table 4

[0386] As shown in Table 4 and Figures 31-34 As shown, the aerosol products of Examples C1 to C4, which use water as the stock solution and nitrogen as the compressed gas, have a jetting force in the range of 10 to 200 mN. The ultrafine bubbles are concentrated in the nanometer range (1 to 1000 nm) with a D90 value of less than 200 nm, and each mL contains 8.0 × 10⁻⁶ mN. 7 More than one ultrafine bubble.

[0387] Additionally, as shown in Table 4 and Figures 35-36 As shown, the aerosol products of Examples C5 to C6, which use water as the compressed gas and carbon dioxide gas as the stock solution, have a jetting force in the range of 20 to 250 mN. The ultrafine bubbles are concentrated in the nanometer range (1 to 1000 nm) with a D90 value of less than 250 nm, and each mL contains 1.0 × 10⁻⁶ m³ / s. 8 More than one ultrafine bubble.

[0388] On the other hand, as shown in Table 4 and Figures 37-38As shown, in Comparative Example C1, which used only water, the number of particles in 1 mL of liquid (water) was 6.25 × 10⁻⁶. 6 The number of particles was relatively small. Furthermore, although the jetting force of the product in Comparative Example C2, which used a pump to spray water, was 62 mN, the number of particles per mL was 2.02 × 10⁻⁶. 7 A few.

[0389] Furthermore, as shown in Table 4 and Figure 39 As shown, the aerosol product of Comparative Example C3, which uses the injection button with a flow adjustment mechanism described in Patent Document 1, has an injection force of 8 mN. Furthermore, the aerosol product of Comparative Example C3 also exhibits numerous bubbles with a particle size exceeding 300 nm (e.g., 800 nm), and a D90 of 680.6 nm. This flow adjustment mechanism has a piston and a spring between the mounting hole and the injection hole. By changing the size of the connecting hole with the injection hole at the piston's position, the flow rate can be adjusted. Therefore, it can be considered that because the contents received from the valve stem are injected through the piston while overcoming the spring's pressure, the pressure loss is large, the injection force is significantly suppressed, and the contents passing through the connecting hole easily generate bubbles, with an increase in bubbles exceeding 300 nm.

[0390] Additionally, as shown in Table 4 and Figure 40 As shown, the aerosol product of Example C7, which uses ethanol as the stock solution and carbon dioxide gas as the compressed gas, has a jetting force of 323 mN. The ultrafine bubbles are concentrated in the nanoscale (1-1000 nm) within a small range with a D90 of less than 200 nm, and contain 4.81 × 10⁻⁶ particles per mL. 7 Each ultra-fine bubble.

[0391] On the other hand, as shown in Table 4 and Figures 41-42 As shown, in the liquid (ethanol) of Comparative Example C4, which used only ethanol, although the ultrafine bubbles were nanoscale (1–1000 nm), the particle number in 1 mL was 5.03 × 10⁻⁶. 4 The number of particles was extremely small. Although the jetting force of the product from Comparative Example C5, which used a pump to spray ethanol, was 52 mN, the number of particles per mL was 2.87 × 10⁻⁶. 7 A few.

[0392] (Example C8) Towards Figure 1The pressure vessel shown is filled with water as the stock solution. A valve is then installed on the pressure vessel, through which nitrogen gas is filled. It is stored at room temperature for 3 days to allow some of the nitrogen to dissolve into the water to saturate. Furthermore, the pressure inside the vessel is 0.8 MPa (25°C). Based on the pressure vessel's full fill volume, the amount of water filled, the amount of nitrogen filled, and the pressure, the calculated nitrogen dissolution rate per 1 mL of water is 130 ppm. The valve stem orifice is Φ0.4, the lower orifice of the shell is Φ1.0, there are no transverse holes, and a suction pipe is installed at the bottom of the shell, allowing the stock solution to be sprayed out from the bottom of the pressure vessel. [The last sentence appears to be incomplete and possibly refers to a valve installation.] Figure 1 The spray button (spray orifice: Φ0.36) shown has diffusion channels (number of channels: 4) and converging channels (number of channels: 4) to produce an aerosol product. 20 mL of the resulting aerosol product was sprayed from the aerosol product into another cup-shaped container, generating and dispersing ultrafine bubbles to create a spray. The spray rate at 25°C was 1.0 g / s.

[0393] (Example C9) Installation of aerosol products in Example C8 Figure 2 The spray button (spray hole: Φ0.60, number of channels for converging: 4) was activated and sprayed into other containers, creating a jet. Furthermore, the pressure inside the container was 0.8 MPa (25°C), and the spray rate was 3.7 g / s.

[0394] (Example C10) Installation of aerosol products in Example C8 Figure 43 The spray button 8a (spray hole: Φ0.35, passage length: 6mm) was activated and sprayed into other containers, creating a spray. Furthermore, the pressure inside the container was 0.8MPa (25℃), and the spray rate was 2.7g / s.

[0395] (Example C11) Installation of aerosol products in Example C8 Figure 43 The spray button 8a (spray hole: Φ1.2, passage length: 6mm) was activated and sprayed into other containers, creating a spray. Furthermore, the pressure inside the container was 0.8MPa (25℃), and the spray rate was 4.9g / s.

[0396] (Example C12) Installation of aerosol products in Example C8 Figure 3 The spray button 8 (spray hole: Φ0.3, passage length: 10.5mm) was pressed and sprayed into other containers, creating a spray. Furthermore, the pressure inside the container was 0.8MPa (25℃), and the spray rate was 2.1g / s.

[0397] (Example C13) Towards Figure 1The pressure vessel shown is filled with water as the stock solution. A valve is then installed on the pressure vessel, through which nitrogen gas is filled. It is stored at room temperature for 3 days to allow some of the nitrogen to dissolve into the water to saturate. Furthermore, the pressure inside the vessel is 0.8 MPa (25°C). Based on the pressure vessel's full fill volume, the amount of water filled, the amount of nitrogen filled, and the pressure, the calculated nitrogen dissolution rate per mL of water is 130 ppm. The valve stem orifice is Φ0.3, and the lower orifice of the shell is also Φ0.3. There are no horizontal holes. A suction pipe is installed at the bottom of the shell, allowing liquid to be sprayed out from the bottom of the pressure vessel. [The last sentence appears to be incomplete and possibly refers to a valve installation.] Figure 1 The spray button (spray orifice: Φ0.36) shown has diffusion channels (number of channels: 4) and converging channels (number of channels: 4) to produce an aerosol product. 20 mL of the resulting aerosol product was sprayed from the aerosol product into another cup-shaped container, generating and dispersing ultrafine bubbles to create a spray. The spray rate at 25°C was 0.9 g / s.

[0398] (Example C14) Towards Figure 1 The pressure vessel shown is filled with 90g (90% by mass) of water as the stock solution, and the valve is fixed to the opening for sealing. Further, 10g (10% by mass) of liquefied petroleum gas is filled from the valve stem, and the valve stem is installed... Figure 3 The spray button shown (spray orifice Φ1.2) was used to create an aerosol product. Using the spray button, 20 mL of the resulting aerosol product was sprayed from the aerosol product into another cup-shaped container, creating a jet. Furthermore, the pressure inside the container was 0.21 MPa (25°C), and the spray rate was 2.3 g / s.

[0399] (Example C15) In addition to using hydrofluoroolefins (HFO-1234ze: trans-1,3,3,3-tetrafluoroprop-1-ene) to replace liquefied petroleum gas, it was installed Figure 1 Except for the spray button (spray orifice: Φ0.3) shown, which has diffusion channels (number of channels: 4) and convergence channels (number of channels: 4), an aerosol product was manufactured using the same method as in Example 14. Figure 1 The spray button ejects the contents into other containers, creating a spray. Furthermore, the pressure inside the container is 0.42 MPa (25°C), and the spray rate is 0.7 g / s.

[0400] (Measurement of jet force) The aerosol products obtained in Examples C8 to C15 were immersed in a constant temperature water bath at 25°C for 30 minutes. The product temperature was then adjusted to 25°C, and the jetting force at a position 5 cm away from the jet orifice was measured using a digital force gauge FGP-0.5 (manufactured by Nidec Shinpo Co., Ltd., Japan). The results are shown in Table 5.

[0401] (Measurement of particle size and number) The aerosol products obtained in Examples C8 to C15 were adjusted to 25°C, and D90, D50, D10, and the number of particles were measured using a nano-tracking particle size analyzer (NanoSight NS300, manufactured by Malvern Panalytical Ltd). Furthermore, the measurements were performed without diluting the sprayed material with solvent. The results are shown in Table 5. Additionally, for Examples C9, C10, C13, C14, and C15, graphs showing the relationship between the particle size and concentration of the sprayed material 15 minutes after spraying each aerosol product are presented in Table 5. Figures 44-48 As shown.

[0402] Table 5

[0403] As shown in Table 5 and Figures 44-46 As shown, the aerosol products of Examples C8 to C13, which use water as the stock solution and nitrogen as the compressed gas, have a jetting force in the range of 10 to 200 mN. The ultrafine bubbles are concentrated in the nanometer range (1 to 1000 nm) with a D90 value of less than 200 nm, and each mL contains 4.0 × 10⁻⁶ mN. 7 More than one ultrafine bubble. Additionally, as shown in Table 5 and... Figures 47-48 As shown, the aerosol products of Example C14 (using water as the raw material and liquefied petroleum gas as the liquefied gas) and Example C15 (using hydrofluoroolefins) exhibit a jetting force in the range of 10–200 mN. The ultrafine bubbles are concentrated in the nanometer range (1–1000 nm) with a D90 value below 200 nm, and each mL contains 4.0 × 10⁻⁶ m³ / s. 8 More than one ultrafine bubble.

[0404] Explanation of reference numerals in the attached figures 1: Aerosol products 2: Pressure-resistant containers 3: Valves 31: Valve mechanism 32: Shell, 32a: Liquid phase inlet hole (or outlet hole) 33: Valve stem, 33a: Valve stem hole, 34: Valve stem rubber, 35: Spring, 36: pipe, 4: Spraying component (or spray button) 5: Operations Department 51: Mounting holes, 52: Ejection hole (or spray hole) 53: First pipeline 54: Branch components 55: Nozzle 6: Spraying component (or spray button) 6a: Operations Department 61: First pipeline 62: Branch components 63: Chimeric part, 64: Cylindrical part 7: Nozzle, 71: Feet 72: Base plate 73: concave part, 74: Internal passageway (or spray passageway) of the ejector component. 7p: Ejection port (or spray port) 8, 8a: Ejection component (or spray button) 81: First pipeline 81a, 81b, 9: Nozzle 81c: Nozzle section 82a, 91: Ejection port (or spray port) 92: Roots L: Liquid (or concentrate) La: liquid phase R: Rotation chamber.

Claims

1. A liquid composition, wherein ultrafine bubbles are dispersed, The volumetric cumulative distribution value of the ultrafine bubbles is 90%, with a particle size (D90) of 50–300 nm. The number of ultrafine bubbles is 4.0 × 10⁻⁶ per milliliter. 7 More than one.

2. The liquid composition according to claim 1, wherein, The ultrafine bubbles are formed by the vaporization of liquefied gas at atmospheric pressure and 25°C. The number of ultrafine bubbles is 5.0 × 10⁻⁶ per milliliter. 7 More than one.

3. The liquid composition according to claim 2, wherein, The liquefied gas includes lipophilic liquefied gas, which is liquefied petroleum gas composed of propane, n-butane, isobutane and mixtures thereof, hydrofluoroolefins with a boiling point below 5°C and mixtures thereof.

4. The liquid composition according to any one of claims 1 to 3, wherein, The liquid composition contains water.

5. The liquid composition according to claim 2, wherein, The liquefied gas contains dimethyl ether.

6. The liquid composition according to any one of claims 1 to 5, wherein, The liquid composition contains a monohydric alcohol having 2 to 3 carbon atoms.

7. A sprayed product, wherein, It is made by filling the liquid composition of any one of claims 1 to 6 into the ejection container.

8. The liquid composition according to claim 1, wherein, The ultrafine bubbles are bubbles of compressed gas.

9. The liquid composition according to claim 8, wherein, The amount of the compressed gas that can dissolve in 1 mL of liquid at 25°C and atmospheric pressure is 0.001 to 5 mL.

10. The liquid composition according to claim 1, 8, or 9, wherein, The liquid composition contains more than 60% by mass of water in the liquid.

11. The liquid composition according to any one of claims 1, 8 to 10, wherein, The liquid composition contains a monohydric alcohol having 2 to 3 carbon atoms.

12. A sprayed product, wherein, It is made by filling the liquid composition of any one of claims 8 to 11 into the ejection container.

13. An aerosol product for spraying liquid compositions, wherein, The liquid composition is a liquid composition in which ultrafine bubbles are dispersed. The volumetric cumulative distribution value of the ultrafine bubbles is 90%, with a particle size (D90) of 50–300 nm. The number of ultrafine bubbles is 4.0 × 10⁻⁶ per milliliter. 7 More than one The aerosol product includes an aerosol container filled with a concentrate and a propellant, and a spray button installed in the aerosol container and having a spray hole formed therein. When the propellant is sprayed from the spray hole, the spray force at a distance of 5 cm from the spray hole is 10 to 400 mN.

14. The aerosol product according to claim 13, wherein, The propellant is a compressed gas.

15. The aerosol product according to claim 14, wherein, The amount of the compressed gas that can dissolve relative to 1 mL of the original liquid at 25°C and atmospheric pressure is 0.001–5 mL.

16. The aerosol product according to claim 13, wherein, The propellant is a liquefied gas.

17. The aerosol product according to any one of claims 13 to 16, wherein, The spray button has a converging passage, in which a groove is formed to converge the sprayed material toward the spray orifice. The number of grooves is 2 to 10.

18. The aerosol product according to any one of claims 13 to 17, wherein, The diameter of the injection hole is 0.2 to 1.0 mm.

Images